This thesis examined a range of methods for sampling soil pore water to investigate the chemistry of trace elements. In particular, the study assessed whether Rhizon samplers, centrifugation, high pressure squeezing and soil suspensions in simulated pore water can be viable approaches for obtaining representative samples of equilibrated soil pore water. Results for metal solubility and speciation were interpreted in terms of both soil morphological effects on trace metal dynamics and artefacts introduced at various stages during sample preparation and handling. The main soil used in the study was an organic-rich sandy silt from a site which has served as a sewage re-processing facility for almost a century. This soil was chosen because of its importance as a long-term repository for metal-enriched sludge applied to arable land, providing a suitable medium on which to study trace metal behaviour. Pore waters were extracted and analysed for major and trace cations and anions, pH, Dissolved Inorganic Carbon (DIC) and Dissolved Organic Carbon (DOC) at two different temperatures (5 degrees Celsius and 15 degrees Celsius), in order to evaluate the extent of bacterial activity, organic decomposition and their consequences on solute composition, during pore water extractions. Speciation was estimated from analysis of pore water chemistry using two software packages (PHREEQCi and WHAM-VI). Pore waters showed different ranges of concentration between the various methods. Different mechanisms and/or chemical reactions were involved during the different extractions; a range of processes was identified, mainly dominated by metal complexation by humus acids and redox reactions. Results revealed that the soil studied was able to partially buffer the free ion activities of the metal ions in pore water with increasing dilutions, but demonstrated virtually no ability to buffer DOC. Identification of the source (i.e. location of pore space) of water extracted was also investigated using water with different isotopic composition (18O/16O). Evidence showed that centrifugation was not able to differentiate between more and less mobile water at FC conditions, rather enhancing the mixing between the two pools of water (native and labelled) by and apparent process of 'infusion'. By contrast, Rhizon samplers appeared to sample water preferentially from the more accessible pool (extra-aggregate), which proved to have a composition showing incomplete mixing with the native water. The results also suggested that mixing of the two pools was rather fast and that was almost completely attained prior to pore water extraction. The study established that the most important factors affecting pore water chemistry during extraction are the conditions to which the samples are exposed during the extraction process. For these reasons Rhizon samplers should be used as a disposable device, and are only applicable for use in high soil moisture soil contents. In contrast, they present no 'side-effects' (providing enough equilibration time) if M2+ (free ion activity) were needed as opposed to Msol (total metal concentration in pore water), as often required in environmental studies. Centrifugation is optimal for bulk solution studies, or when homogenisation represents a key experimental point; targeted studies are also possible. Soil squeezing is subject to severe limitations in the case of prolonged extractions of biologically active soils, due to the effects of anaerobism. Squeezing should only be used for 'fast' extractions of soils. Finally, batch extractions are well suited to studies on M2+ equilibria, but more studies are needed to clarify the effect of soil: solution ratio on metal and DOC solubility.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:514616 |
| Date | January 2005 |
| Creators | Di Bonito, Marcello |
| Publisher | University of Nottingham |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://eprints.nottingham.ac.uk/10123/ |
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