Mechanism of Cd2+ toxicity: Cd2+ inhibits photoactivation of Photosystem II by competitive binding to the essential Ca2+ site

Cadmium (Cd2+) is a well-known highly toxic element. The molecular mechanisms of the Cd2+ toxicity are not well understood. In photosynthetic organisms, toxic Cd2+ concentrations are often in the low-μM range. It has been proposed that low-μM Cd2+ concentrations affect photosynthesis at the level of Photosystem II by inhibiting oxygen evolution. However, in vitro studies on isolated, functional Photosystem II showed that much higher Cd2+ concentrations (mM range) were needed for inhibition. Here we show that Cd2+ in the low-μM range inhibited photoactivation (i.e., assembly of the water splitting complex) in Chlamydomonas reinhardtii and in isolated Photosystem II. Photoactivation is the last step in the assembly of Photosystem II before it becomes functional. The exact Cd2+ concentration necessary for inhibition depended on the concentration of calcium. It is proposed that Cd2+ binds competitively to the essential Ca2+ site in Photosystem II during photoactivation. The low Cd2+ concentration needed to inhibit photoactivation suggests that this event is also involved in the Cd2+-induced inhibition of photosynthesis in vivo. This mechanism is likely to be important for Cd2+ toxicity towards photosynthetic organisms in general, at least in unicellular like C. reinhardtii where Cd2+ has easy access to the photosynthetic apparatus.