Three fibrous amphiboles that are not regulated as asbestos--two from Biancavilla (Sicily, Italy) and one from Libby (MT, USA)--were studied in order to establish relationships between surface chemistry and surface reactivity. The three fibrous samples, plus one prismatic fluoro-edenite from Biancavilla that was used for comparison, were investigated by X-ray photoelectron spectroscopy (XPS) in order to obtain their quantitative surface compositions and to determine the chemical environment of the Fe in each case. In particular, the Fe 2p(3/2) peak was fitted and, for the first for these materials, the binding energies of Fe(II) oxide, Fe(III) oxide and Fe(III) oxyhydroxide were identified. Bulk chemistries and Fe oxidation states were obtained from previous studies for the samples from Biancavilla, and were investigated in the present work by electron microprobe (EMP) and (57)Fe Mössbauer spectroscopy (MS) for the sample from Libby. Comparison between surface and bulk data revealed that the sample with the lowest bulk Fe oxidation state was the one most affected by surface oxidation, while the samples with bulk highly-oxidised Fe were showing very high signal of Fe (III) oxy-hydroxide probably due to weathering. The surface reactivities of the fibrous amphiboles were investigated by measuring the production of the [DMPO, HO]* radical adduct using electron paramagnetic resonance (EPR) spectroscopy. Notably, significant chemical reactivity was observed; it was found to be comparable with--or, for the Libby sample, even higher than--that of fibrous tremolite (one of the six asbestos minerals). A positive linear correlation was observed when the production of HO* radical was plotted versus the Fe(II) content on the fibre surface. Data on fibrous tremolite obtained from previous studies were added to substantiate the correlation. These results provide evidence that Fe(II) at the fibre surface controls the production of radicals at the fibre surface. The observed relationship provides further confirmation that Fe topochemistry is strictly related to--though not solely responsible for--the toxicity of asbestos and other fibrous amphiboles that are not regulated as asbestos.