Despite the suspected biological imprint on the terrestrial silicon (Si) cycle, plant contribution to the Si continental reservoir is poorly quantified. Within the soil-plant system, aqueous silicon (H4SiO40) can be retrieved from soil solution by plant uptake, clay formation and adsorption onto secondary oxides, or leached out and transferred to stream waters. Two approaches are very promising to trace Si within the soil-plant cycle: the Si stable isotopes and Ge/Si ratio. This thesis aims at quantifying the Si isotopic fractionation induced by plants and soil processes in both controlled (in vitro) and natural conditions (in situ). The model used is a tropical soil-plant system involving a Si-accumulating plant (banana, Musa acuminata Colla, cv Grande Naine) cropped on soils derived from basaltic ash but differing in weathering stage (Cameroon, West Africa). Si isotopic compositions in the different compartments of the soil-plant system were measured by MC-ICP-MS in dry plasma mode with external Mg doping. The analytical method required specific developments, and was validated by an inter-laboratory comparison of reference materials. Plant root uptake of Si, and Si transport within the plant induce an isotopic fractionation quantified in vitro and measured in situ. The plant Si isotopic signature is influenced by soil weathering stage, precisely by soil contents of clay and iron oxide. Soil clay-sized fractions sequestrate light Si isotopes following abiotic fractionating processes of mineral weathering and clay formation, leaving a residual solution enriched in heavy Si isotopes. Biogenic Si, enriched in light Si isotopes, constitutes a Si source for clay formation. Clay-sized Fe-oxides concentrate with increasing weathering and soil development. They selectively adsorb light Si isotopes by surface complexation of monomeric H4SiO40. Silicon transport within the plant produces a Ge/Si fractionation involving Ge sequestration in roots whereas weathering and clay formation induce a selective Ge sequestration in clay minerals, producing an increased Ge/Si ratio with increasing weathering, in excellent agreement with Si isotopic data. In the soil-plant system studied, Si stable isotopes thus trace three major continental processes: plant uptake and phytolith formation, sequestration of Si in clay minerals, and adsorption of Si by Fe-oxides. These biotic and abiotic processes all lead to a progressive enrichment of pore waters in heavy Si isotopes.

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The thesis reviews literature relating to lead in the environment with particular reference to the distribution and pathways of lead in the soil and plant ecosystem. Methods of conducting large area soil surveys and assessing the distribution of lead and other heavy metals including cadmium, copper and zinc are also examined. A survey was conducted over a 370 km2 area of North East Derbyshire, England. Maps showing the distribution of the metals reveal anomalously high concentrations related in many instances to past industrial activity. A simple reliable and rapid acid digestion procedure was developed and the procedure evaluated through an interlaboratory survey involving 22 laboratories. This demonstrated that analysts should seek to improve analytical performance through achieving better interlaboratory correlation rather than intralaboratory precision. A stratified random sampling protocol was developed and evaluated which allowed an estimate of precision to be placed on the results of the trace metal soil survey. An assessment was carried out of the contribution that lead fromaerially deposited dust and soil sources makes to the distribution of lead in potato plants. A micro sampling cup technique was developed which permitted (for the first time as far as can be ascertained) the analysis of lead in discrete sections of solid plant tissue from single plants grown under field conditions. This overcomes the problems of sensitivity which normally requires that samples are bulked or dosed with lead salts. Results are presented for the distribution of lead in potato plants grown in several field locations and in soils containing varying concentrations of lead. The major source of lead in the plants via the soil with aerial sources having a negligible effect on tissue distribution. Comparisons are made between results obtained by conventional flame atomic absorption spectrometry and the microsampling cup procedure.

Salt affected soils and their effects on land and water resources have been identified as one of the most severe environmental problems facing Australia. This current study focused on the incorporation of recycled organic products (RO) into an acidic saline soil that had been irrigated with an industrial effluent (IE), specifically to investigate the potential for these organics to be used in rehabilitation. Compost incorporated into the acidic saline soil was able to raise pH to more favourable levels required for plant growth (pH 6 – 7.5). Plant growth was however dependent on the input material of the compost as well as the irrigation scheme. The soils amended with this compost generally showed higher and more rapid microbial activity, measured by CO2 emissions, in all amendment rates than the plant derived compost. Overall it could be concluded that the application of RO on saline soils improved the establishment and growth of plants and alleviated to some degree the negative effects of IE. However great care should be taken at the selection of the input material, as high rates of ammonium, calcium and other soluble salts can increase the EC of an amended soil further.

Ecological stoichiometry is a useful tool for understanding of ecological dynamics and related processes. There are only rare informations about nutrient cycling and nutrient dynamics in plant- soil system in restoration areas after coal mining. Different plant species have developed own strategies and treat differently with nutrients which can influence nutrient cycling and consequent nutrient return to the soil. In thesis, I investigated ecological stoichiometry as one of key factors which controls soil development in post mining sites. In general introduction, known facts are summarized about e.g. plant traits, decomposition process, nutrient cycling and consequences for soil development and restoration practices. But still, relationship between leaves, plant litter, and soil is poorly understood in restoration areas. The results of a doctoral thesis are presented in five papers, out of which three have been published, one has been already submitted and one manuscript is prepared for publication in an international journal with impact factor. In the first presented publication, the influence of soil fauna was studied (especially earthworms) on soil development. Soil development differed significantly between sites afforested with different tree species and it is strongly influenced by the...

The understanding of the spatial distribution of lead (Pb) in soil is important in the assessment of potential risks and development of remediation strategies for Pb contaminated land. In situ heterogeneity of Pb was measured at two heavily contaminated sites in the United Kingdom using the Portable X-ray Fluorescence Spectrometer (P-XRF) over a range of spatial scales (0.02 to 50 m). The pattern of the distribution of Pb was very variable, and when expressed as heterogeneity factor (HF), it ranged from 1.2 to 3.2 (highly heterogeneous). The effect of such Pb heterogeneity on plant uptake was investigated in greenhouse pot trials. Two earlier pot trials, which assessed the effect of Pb in a fixed concentration (1000 mg/kg) and in a range of concentration (100 to 10000 mg/kg) found a significant effect of the Pb added treatments, when compared to a control treatment (0 mg/kg Pb added). Biomass and uptake varied by 20 to 100% within and between 16 species/varieties. Results enhanced the selection of two species (Brassica napus and Brassica juncea) for further pot trials. A third pot experiment with Brassica napus and Brassica juncea in simplistic binary model of heterogeneity found 20 to 60% lower uptake in the binary treatment, than homogeneous the treatment. Biomass was higher by 10 to 50% in Brassica juncea and 20 to 40% lower for B. napus in the bianary treatment, when compared to the homogeneous and control treatments. The effect of a more realistic in situ heterogeneity on plant uptake was investigated in a further pot trial, which simulated low (LH), medium) (MH) and high (HH) heterogeneity treatments, compared to a homogeneous (HO) treatment. It detected a significant (P < 0.05) impact of heterogeneity on biomass and uptake between treatments and species. Four to five fold lower biomass were recorded in HH treatment, when compared to the HO treatment. Shoot and root uptake in (mg/kg) concentration increased with increasing heterogeneity with peak uptake (twice as high as HO treatment) in LH for B. napus and in HH and MH treatments for B. juncea respectively. Shoot and root Pb masses in (μg) were maximum in HO and MH treatments respectively with 50 to 70% lower Pb mass in the HH treatment. Results showed that response to heterogeneity is species specific. A sub-experiment explored the behaviour of plant roots in HH treatment and found 20 to 80% variation in root biomass between concentric patches with same nominal soil Pb concentrations. This provided insights into varied responses of these species to realistic Pb heterogeneity. The research demonstrated that the presence and extent of in situ heterogeneity of Pb in soil plays an important role in Pb uptake by plants. It also showed that the homogeneous and simplistic binary model of heterogeneity do not give reliable estimates of plant growth and Pb uptake in realistic field conditions. This work has implications for improving the efficiency of phytoremediation of Pb contaminated land, phytomining, reliability of risk assessment and models of human exposure to Pb.

Heterogeneity of contaminants in soils can vary spatially over a range of scales, causing uncertainty in environmental measurements of contaminant concentrations. Sampling designs may aim to reduce the impact of on-site heterogeneity, by using composite sampling, increased sample mass and off-site homogenisation, yet they could overlook the small scale heterogeneity that can have significant implications for plant uptake of contaminants. Moreover, composite sampling and homogenisation may not be relevant to target receptor behaviour, e.g. plants, and studies, using simplistic models of heterogeneity have shown that it can significantly impact plant uptake of contaminants. The alternative approach, to accept and quantify heterogeneity, requires further exploration as contaminant heterogeneity is inevitable within soils and its quantification should enable improved reliability in risk assessment and understanding variability in plant contaminant uptake. This thesis reports the development of a new sampling design, to characterise and quantify contaminant heterogeneity at scales, from 0.02m to 20m, using in situ measurement techniques, and 0.005m to 0.0005m, using ex situ techniques. The design was implemented at two contaminated land sites, with contrasting heterogeneity based upon historic anthropogenic activity and showed heterogeneity varying between contaminants and at different spatial scales, for Pb, Cu and Zn. Secondly, this research demonstrates how contaminant heterogeneity measured in situ can be recreated in a pot experiment, at a scale specific to the plant under study. Results, from 4 different plant species, demonstrated that existing simplistic models of heterogeneity are an inadequate proxy for plant performance and contaminant uptake under field conditions, and significant differences were found in plant contaminant concentrations between simplistic models and those based upon actual site measurements of heterogeneity. Implications of heterogeneity on plant roots were explored in the final experiment showing significant differences in root biomass between patches of differing contaminant concentrations.

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In recent years, the Soil-Plant-Atmosphere (SPA) continuum has faced unprecedented challenges due to anthropogenic modifications and climate change. Understanding the complex dynamics of this system in response to such changes is crucial for addressing contemporary environmental concerns. Albert Einstein's famous quote, "The measure of intelligence is the ability to change", resonates deeply throughout this doctoral thesis. This thesis aims to address the complex issue of SPA interactions by developing a comprehensive set of models capable of representing the intricate dynamics of this system. At the core of this research lies the integration of sophisticated descriptions of hydrological and plant biochemical processes into a novel ecohydrological model, GEOSPACE-1D (Soil Plant Atmosphere Continuum Estimator model in GEOframe). Through a combination of theoretical exploration, engineering methodologies, and empirical experiments, this thesis aims to advance our understanding of SPA interactions. The development of adaptable models, represents a significant contribution to the field. The thesis emphasizes the practical implications of employing models to analyze experimental data, thereby enhancing our comprehension of various phenomena. In conclusion, this thesis provides valuable insights into SPA interactions and lays the groundwork for future research and applications. By embracing the challenge of understanding and modeling the SPA continuum, this work contributes to the ongoing efforts to address environmental challenges and promote sustainable practices.

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