Summary. Excised roots from aeroponic axenically 48 h dark-grown sunflower (HeIianthus annuus L.) seedlings showed redox activities, being able to oxidize/reduce all the exogenously added electron donors/acceptors, that affected the H+/K + net fluxes simultaneously measured in the medium. Trials were performed with in vivo and CN--poisoned roots; these showed null H+/K + net flux activity but still oxidized/reduced all the e-donors/acceptors tested except NADH. NADH enhanced the rate of H + efflux by in vivo roots, otherwise not changing any of the normal flux kinetic characteristics, suggesting that NADH donates e-and H + to the exocellular NADH oxidoreductase activity of a CN--sensitive redox chain in the plasmalemma of the root cells. K + influx was not affected, probably because the NADH concentration was not very high. The e-donor HFC(hexacyanoferrate)(II) activated the H + efflux in a very different way: maximum H + effiux rate was maintained, but both the maximum rate plateau and the optimal pH range were extended, and hence the total H + efflux was significantly enhanced. At the same time, the K + influx was doubled. The different H+-efflux kinetics, together with the small but significant HCF(II) oxidation by CN--poisoned roots, were taken as evidence that, besides the CN--sensitive redox chain, an alternative CN--resistant redox chain in the plasmalemma was involved in HCF(II) oxidation. The effect of the oxidized form HCF(III) on H + and K + fluxes was the opposite to that described for HCF(II), but the other H + efflux kinetic characteristics were similar (the maximum rate plateau was extended so that total H + efflux equaled that of the controls). It is proposed that HCF(III) accepts e-only from the alternative CN -resistant redox chain. We could not measure the effect of HCI(hexachloroiridate)(IV) on H + efflux, as the pH electrodes alone quickly reduced the compound. HCI(IV) promoted a rapid transitory K + efflux, followed by recovery of K + influx. The HCI(IV) reduction by in vivo or CN--poisoned *Correspondence and reprints: U. E. FisioIogfa Vegetal, Facultad de Ciencias, Universidad de Extremadura, Campus Avda. Elvas s/n, E-06071 Badajoz, Spain. roots was extremely rapid, following similar kinetics. Thus, only the CN--resistant redox chain was involved in both cases. The redox chain inhibitor cis-ptatinum(II) annulled ion fluxes in the presence of both NADH and HCF(III), and later even inverted them (a small H + influx down the gradient would induce K § efflux). Cis-platinum(II) did not affect HCF(III) reduction by in vivo roots, and only slightly depressed that by CN--poisoned roots. Overall, the effects of the exogenously added e-donors/acceptors tested were consistent with the existence of a CN--resistant redox chain in the plasmalemma of the root cells which would donate/accept e even when the H + and K + fluxes were annulled by CN or even inverted by cis-platinum(II) treatments. Thus, in the ptasmalemma of in vivo roots this chain would compete for electrons with the normal CN--sensitive on...