Chapter 1 of this thesis is a general review of published work o_ the origins and distribution of Cd, Cu, Fe, Mn and Zn in soils and their uptake and functions in plants. Chapter 2 is a synopsis of the geological history of the Fayoum of relevance to the origins of sediments at the study sties. Previous fractionation procedures, and a proposed modification to improve the determination of carbonate-bound elements are discussed in Chapter 3, while other analytical procedures are described in Chapter 4. Results of general soil analyses, of the fractionation analyses and useful correlation matrices, are tabulated together (for convenience in Chapter 5) and are discussed in detail in the following chapter. Texture was a crucial factor, finer-textured soils generally having lower pH and higher organic matter contents, although the latter were generally greater closer to the surface. Clay and silt contents were highly correlated, probably reflecting water sorting in the Fayoum, which aided the texture/drainage effect. Drainage (i.e. texture) was apparently very important in the fractionation chemistry of elements influenced by redox-reactions, i.e. Fe and Mn, and elements for which distribution depended upon Fe and Mn oxides (e.g., Zn) to a significant extent. Clay was especially important to the concentration of crystalline and amorphous iron oxides. Cd and Cu showed marked surface accumulation, especially in the exchangeable fractions, for many profiles, probably through pollution. The Cu content of organic matter was strikingly uniform at the Fayoum. Amorphous and crystalline Fe oxides seem to be especially important in the distribution of Zn. Clay Cd, Fe and Zn and, to a lesser extent, Cu and Mn contents were relatively constant, suggesting uniform origins. Chapter 7 describes a pot experiment on the soils using barley as a test crop, aimed at relating uptake to the fractionation results. Interpretation was complicated by a dominant effect of soil salinity. Chapter 8 suggests future related research.

Soil samples from 118 sites on 71 geologic units in southwest Oregon were collected and analyzed to determine the background concentrations of metals in soils of the region. Sites were chosen in areas that were relatively undisturbed by human activities. The U.S. Environmental Protection Agency approved total-recoverable method was used to recover metals from samples for analysis. The twenty six metals analyzed were: Ag, AI, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, La, Li, Mg, Mn, Mo, Na, Ni, Pb, Sb, Se, Tl, V and Zn. The Klamath Mountains followed by the Coast Range contain the highest soil concentrations of AI, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Ni, V and Zn. Soils of the Coastal Plain and High Lava Plains contain the lowest concentrations of these metals. Unusually high soil As concentrations are found at two sites in the Klamath Mountains. All Be and Cd values above laboratory's reporting limits are also from the Klamath Mountains and Coast Range. Concentrations of soil Ba and La are fairly uniform throughout the region. Soil Pb levels are generally low with a few exceptions in the Klamath Mountains, Coast and Cascade Ranges. The region west of the Cascade Range has higher soil Hg contents than in the east. Soil metal concentrations are generally much higher in the region west of the Cascade Range, excluding the Coastal Plain, than in the east with the exception ofNa, because of more ultramafic rocks and a wetter climate. Soil metal concentrations are directly related to soil development with the highest concentrations being found in well developed Alfisols and Ultisols and the lowest concentrations in poorly developed Entisols. Most metals have similar averages and ranges of concentration compared to the rest of the United States (U.S.). Metals with high values compared to the rest of the U.S. are Cr, Co, Cu, Mn and Ni. In general, AI, Co, Cr, Cu, Fe, La, Li, Mg, Na, Ni, and V are concentrated in the B horizon while Ba, Ca, Hg, K, Mn, Pb and Zn are concentrated in the A horizon.

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The research used dendro-chemical analysis of ash tree rings and current year leaf litter to track Cd, Pb, Zn, Cu, Mn, Cr, and Sn spread and cycling from a closed garbage dump-toxic waste site. This technique allowed for determination of areal extent, contaminant levels and time period of initial contaminant contact. Only Zn, Sn, and Cu were found in elevated quantities in the xylem wood and Pb in the leaf litter. Elemental concentrations of Pb, Sn and Cd in xylem wood and leaves of ash were positively correlated. Tin was the only element to demonstrate a clear initial contact period and elemental accumulation with age. Significant levels of Cu accumulated in the heartwood while Zn revealed significant but inconsistent accumulated patterns. Expected attenuation zones associated with municipal solid waste landfill leachate dispersion were not found; thus the pathway for contaminant dispersion was likely through groundwater flow. / An elemental index was developed to facilitate the use of dendro-chemical analysis in periods of suppressed tree growth resulting from environmental pollution.

Innovative means and methods were tested to develop an economical, pragmatic and environmentally sustainable soil remediation process for heavy metal contaminated soils. An unsaturated-flow soil washing procedure was devised to dissolve the soil-bound toxic heavy metals; the latter were extracted by a chemical washing solution that percolated through the soil matrix. Subsequently, the leached toxic heavy metals were selectively concentrated, by a chemical precipitation process, into a solid waste. Thereby, a fraction of the spent ethylenediaminetetraacetic acid (EDTA), within the washing and rinsing leachate, was theoretically regenerated and recycle-ready. / The unsaturated-flow washing procedure was perfected by applying different treatments to a soil from a secure landfill. This soil was contaminated with Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, S and Zn. The major contaminants were Fe, Pb, Zn, S, Cu and Mn, making up 25, 1.9, 1.0, 0.4, 0.4 and 0.2%wt of the soil. The extraction responses of the contaminants and those of Al, Ca, Mg and P were established for citric acid (0.5 M) and different molarities of diammonium EDTA ((NH4)2EDTA). The DOW Chemical Company supplied the (NH4)2EDTA (i.e. VERSENE), a 1.37M industrial cleaner, which roughly costs $1.85kg-1 in bulk. The affordability of VERSENE was a pre-condition for hoping to satisfy the economical feasibility of remediating trace metal contaminated soils. / Ultimately, the developed unsaturated-flow washing procedure was tested in a pilot-scale experiment, for its ability to remediate a soil from an abandoned car battery recycling facility. The latter soil was severely contaminated with Pb (3.9%wt). Drip irrigation was used to apply (NH4) 2EDTA and water-rinsing solutions to the surface of soil heaps that rested atop an impermeable barrier, which permitted the retrieval of the leachate. A cumulative EDTA input to the soil of 10.6% wt extracted 49.4% of the total Pb content of the soil. Alternatively, readily biodegradable citric acid barely extracted 2.2% of the total Pb content of the soil, for a cumulative input of 18.1% weight of soil. Different treatments were tested for their effectiveness in concentrating the leached toxic heavy metals into a solid waste. The Pb was best precipitated with Na2S alone, as it provided the most concentrated solid toxic waste. / The environmental sustainability of remediating trace metal contaminated soils was thoroughly examined, as per the amounts of chemical entrants and toxic waste by-products, and per the post-treatment leaching of toxic levels of the remaining and potentially toxic trace metals. (Abstract shortened by UMI.)

The adsorption behaviour of trace metals in soil may provide us with a way to more accurately predict and assess the toxicity of metals in the environment. This thesis reports efforts to apply surface complexation modeling to agricultural and forest soil and to relate model parameters to common soil properties. This study considered Ca, Cd, Cu, Pb and Zn but the methods here could be applied to other metals. In Chapter 2, the surface charge and adsorption behaviour of a set of Ap horizons was characterised using back-titration and batch adsorption techniques. With the objective of simplifying the application of the NICCA model to surface charge and cation adsorption in whole soils the parameters of the NICCA model were related to soil properties (Chapter 3). Four of the six surface charge parameters could be predicted from soil properties and this enabled me to reasonably predict the surface charge of a second group of soils from soil properties. These results suggest that it is possible to make reasonable predictions about the surface charge and adsorption behaviour of a given type of soil using some easily measurable soil properties and a set of generic NICCA adsorption parameters for that soil type. In Chapter 4 this idea is applied to the determination of lime requirement for the agricultural soils.

Soil quality guidelines are currently based on total trace metal loads. There is a need to define indices of bioavailability to allow reasonable predictions for plant metal uptake and toxicity in soils. Trace metal toxicities to plants often correlate best with free metal ion activities. The first objective was to develop a plant bioassay that is sensitive to trace metals at concentrations realistic for soils. The root elongation of lettuce Lactuca sativa 'Buttercrunch' was used as toxicological endpoint. This endpoint was sensitive and reproducible to environmentally relevant concentrations of Cd, Cu, Ni, Pb and Zn. The second objective was to test whether free metal ion activities are constant predictors of metal toxicities in synthetic solutions and in soil extracts that differ in their concentrations of cations and ligands. The root elongation assay was used to test this hypothesis. In synthetic solutions, the rhizotoxicity of Cd, Cu, Ni, Pb and Zn decreased with increasing Ca and H concentrations. This could not be explained with the effect of higher cationic concentrations on root growth or on solution speciation. It was concluded that Ca and H inhibited the rhizotoxicity of all metals tested. The rhizotoxicity of Cu and Cd was further examined in soil extracts. Both metals became less rhizotoxic at higher H and dissolved organic matter concentrations. The rhizotoxicity endpoints from the experiments in synthetic solution were used to develop parameters for a Biotic Ligand Model (BLM) for Cd, Cu, Ni, Pb and Zn. The BLM accounts for solution speciation and interprets cationic inhibition of rhizotoxicity as competition of metals with Ca and H for potential sites of rhizotoxicity. The BLM predicted metal rhizotoxicity better than the free metal ion activity in synthetic solutions and in soil extracts. Different models were tested against literature rhizotoxicity data for metals at different Ca and H concentrations. Predictions for metal rhizotoxicity given by BLM, Gouy-Chapman-Stern model and Freundlich equation model were compared with predictions based on free metal ion activities in solution. The BLM predicted rhizotoxicity most accurately. The BLM seems promising for predictions of metal toxicity and metal bioavailability in soils to support site-specific environmental risk assessments.

Trace elements added to the soil by human activities could contaminate it and occasionally cause a threat to environmental and human health. The toxicity and mobility of a trace element are affected by the element's solubility, which in turn is influenced by the soil properties. When mobile, trace elements can be leached out of the soil. If leaching occurs at a faster rate than atmospheric deposition, element concentrations in the soil will decrease by natural attenuation. / We analyzed soil properties in 40 soils and their soil solutions to obtain a set of equations with the most significant predictors of As, Cd, Co, Cu, Mo, Ni, Pb and Zn in solution. The total element concentration and the pH were the best predicting variables of the amount of element in solution for all trace elements analyzed, while organic carbon and Al or Mn oxides also influenced the solubility of some trace elements. Using the equations predicting elemental solubility, we wrote a model for natural attenuation in the computer program Stella that considers atmospheric deposition as the input for trace elements and leaching as the output. Simulations were carried out for the 40 soils during 1,000 years with steady deposition inputs. / At current atmospheric deposition rates and the neutral to alkaline pH of these soils, attenuation occurred in most soils for Mo. For As, Cd, Co, Cu and Ni it occurred only in soils with abundant total element concentrations or an acidic pH. Minor retention occurred with Pb and Zn. Only Cd and Cu were of concern in leaching waters. The developed model can serve as a decision making tool in the selection of natural attenuation as a remediation strategy.

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