Sporopollenin exine capsules (SECs) derived from plant spores and pollen grains have been proposed as adsorption, remediation and drug delivery agents. Despite many studies there is scant structural data available. This X-ray absorption investigation represents the first direct structural data on the interaction of metals with SECs and allows elucidation of their structure-property relationships. Fe K-edge XANES and EXAFS data have shown that the iron local environment in SECs (derived from Lycopodium clavatum) reacted with aqueous ferric chloride solutions is similar to that of ferrihydrite (FeOOH) and by implication ferritin. Fe Kα XRF micro-focus experiments show that there is a poor correlation between the iron distribution and the underlying SEC structure indicating that the SEC is coated in the FeOOH material. In contrast, the Fe Kα XRF micro-focus experiments on SECs reacted with aqueous ferrous chloride solutions show that there is a very high correlation between the iron distribution and the SEC structure, indicating a much more specific form of interaction of the iron with the SEC surface functional groups. Fe K-edge XANES and EXAFS data show that the Fe II can be easily oxidised to give a structure similar to, but not identical to that in the Fe III case, and that even if anaerobic conditions are used there is still partial oxidation to Fe III . CREATED USING THE RSC ARTICLE TEMPLATE (VER. 3.0) -SEE WWW.RSC.ORG/ELECTRONICFILES FOR DETAILS ARTICLE TYPE www.rsc.org/xxxxxx | XXXXXXXX 2 | Journal Name, [year], [vol], 00-00 ](ragweed with magnetite prepared from FeCl2 and FeCl3) have been proposed as a method for the removal of organic pollutants from aqueous media, 44 and those derived from Candida rugosa have shown excellent enatioselectivity. 45,46 Despite the large amount of work carried out on metal sorption and coordination to SECs there are very few reports on the nature of the interaction between the metal ions and the sporopollenin itself. It is important to understand how such conjugates are capable of fulfilling their roles to enable insights into new potential applications such as solid supports for metal catalysts. X-ray absorption spectroscopy (XAS) is able to probe the local structural environment around the element of interest. When carried out using micro-focus instrumentation it can provide both structural and chemical state imaging data from single exines. This approach has been used previously at the Fe K-edge to study geological [47][48][49][50][51] and soil samples, 52,53 archaeological specimens, 54-59 biological tissues [60][61][62][63][64][65][66][67][68] and cometary material. [69][70][71][72] Whilst there has been some X-ray absorption work on sporopollenin using the C K-edge (ca. 290 eV), which identified ketonic groups on the surface of the pollen grain and aliphatic carbon across the whole structure, 73 there appears to be no XAS experiments carried out at the metal K-edges in the literature. In this work we report an Fe K-edge XANES and EXAFS as well as an Fe Kα X-ray fluoresc...