At the heart of long term sustainable soil management is chemical fertility through the retention of exchangeable cations. Many current concepts of cation exchange and its relationship with base cation availability remain unchanged over the past century. Despite considerable advancements in analytical techniques many methods used today would be familiar to our forefathers. Comparative studies were undertaken in this thesis to understand how techniques to measure exchangeable soil ions could be enhanced and matched to defined scenarios. The total amount of cations that can be retained electrostatically on soil surfaces is termed the cation exchange capacity (CEC). An ability to systematically and consistently measure CEC is an essential step in soil characterisation. Compulsive exchange methods (using either 1.0 M NH4OAc or 0.05 M BaCl2) at a fixed pH value for determining CEC were scrutinised but acknowledged to be prone to systematic artefacts. The relationship between soil pH, soil texture and CEC was soil specific. When the batch method was compared with the column leach method, the former was more consistent for all soils. For calcareous soils BaCl2 was more suitable but NH4OAc was more generally applicable. The CEC was consistently significantly greater by the compulsive technique when compared with the effective method. The NH4OAc extraction method was applied to soils contaminated with potentially toxic elements (PTEs). The exchangeable concentration of PTEs correlated with total PTE loading. However, the exchangeable Ca decreased with amendment rate confirming an exchange of sites by PTEs. The compulsive technique extracted PTEs that were significantly 2 negatively correlated with soil basal respiration, phosphatase activity, potential nitrification rate (PNR) and the soil microbial biomass carbon. This confirms that of this method is evaluating the bioavailable/bioreactive fraction. Soil cation exchange capacity and exchangeable base cations increased commensurate with the amendment loading of bentonite and charcoal. The exchange capacity was also soil specific. Following amendments, the exchange capacity was higher after six weeks than after thirty weeks. This means that the amendment performance became impaired with time perhaps as the fine soil particles coated the ameliorant causing a decline in CEC. The difference between the effective and compulsive CEC was described as the calculated CEC. This was very sensitive to soil pH and was confirmed in a detailed study at a site where pH plots were amended over a five decade period. As pH rose, so did the exchangeable fraction of Ca, Mg and K. As the pH declined, Al, Fe and Mn exchangeability increased. Extraction techniques must be sympathetic of the soil pH value. The quantification and characterisation of exchangeable cations remains as fundamental a component of soil science today as it was a century ago.