Synopsis: ZONED spherulites in greenalite-siderite-silica rocks of the Emilia-San Valentin lead-zinc deposit, Sierra de Cartagena, SE Spain, show a core of iron-rich talc, (Mg_l.8Fe_l.2)Si₄O_l0(OH)₂, an intermediate zone of opal-chalcedony, and a rim of minnesotaite, (Fe_2.7Mg_0.3)Si₄O_l0(OH)₂. Crystalllization of the spherulites, presumably from undercooled silica sols carrying dissolved Mg and Fe, began with the non-equilibrium precipitation of metastable iron-rich talc; the residual fluids enveloping the growing spherulites became more iron-rich in composition until metastable equilibrium between iron-rich talc and iron-enriched residual liquid impeded the further growth of the iron-rich talc; the spherulites were then overgrown by colloidal silica flocculates and a rim of minnesotaite precipitated from the iron-enriched residual fluid. The proposed crystallization model implies that, if talc and minnesotaite represent an isomorphic series, under equilibrium conditions there is a broad immiscibility region in the series.