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To identify at the atomic level the source of toxicity in asbestos, the effect of progressive iron loading on a synthetic iron\u2010free model nanofibre previously found non\u2010toxic in cellular tests was studied. A set of five synthetic chrysotile nanofibres [(Mg,Fe)<jats:sub>3<\/jats:sub>(Si<jats:sub>2<\/jats:sub>O<jats:sub>5<\/jats:sub>)(OH)<jats:sub>4<\/jats:sub>] has been prepared with Fe ranging from 0 to 1.78\u2005wt\u2009%. The relationship between fibre\u2010induced free\u2010radical generation and the physico\u2010chemical characteristics of iron active sites was investigated with spin\u2010trapping techniques on an aqueous suspension of the fibres and M\u00f6ssbauer and EPR spectroscopies on the solids, respectively. The fully iron\u2010free fibre was inert, whereas radical activity arose with even the smallest amount of iron. Surprisingly, such activity decreased upon increasing iron loading. M\u00f6ssbauer and EPR revealed isolated iron ions in octahedral sites that undergo both axial and rhombic distortion and the occurrence of aggregated iron ions and\/or extra\u2010framework clustering. The isolated ions largely prevailed at the lowest loadings. Upon increasing the loading, the amount of isolated iron was reduced and the aggregation increased. A linear relationship between the formation of carbon\u2010centred radicals and the amount of rhombic\u2010distorted isolated iron sites was found. Even the smallest iron contamination imparts radical reactivity, hence toxicity, to any chrysotile outcrop, thereby discouraging the search for non\u2010toxic chrysotile. The use of model solids that only differ in one property at a time appears to be the most successful approach for a molecular understanding of the physico\u2010chemical determinants of toxicity. Such findings could also be useful in the design of safer nanofibres.<\/jats:p>","DOI":"10.1002\/chem.201001893","type":"journal-article","created":{"date-parts":[[2010,11,24]],"date-time":"2010-11-24T10:42:24Z","timestamp":1290595344000},"page":"350-358","source":"Crossref","is-referenced-by-count":70,"title":["The Iron\u2010Related Molecular Toxicity Mechanism of Synthetic Asbestos Nanofibres: A Model Study for High\u2010Aspect\u2010Ratio Nanoparticles"],"prefix":"10.1002","volume":"17","author":[{"given":"Francesco","family":"Turci","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maura","family":"Tomatis","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Isidoro G.","family":"Lesci","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Norberto","family":"Roveri","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bice","family":"Fubini","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2010,11,24]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1186\/1743-8977-6-28"},{"key":"e_1_2_6_2_2","unstructured":"C.\u2005L. 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