Phosphorus is an essential building block of life, likely since its beginning. Despite this importance for prebiotic chemistry, phosphorus was scarce in Earth's rock record and mainly bound in poorly soluble minerals, with the calcium-phosphate mineral apatite as key example. While specific chemical boundary conditions have been considered to address this so-called phosphate problem, a fundamental process that solubilizes and enriches phosphate from geological sources remains elusive. Here, we show that ubiquitous heat flows through rock cracks can liberate phosphate from apatite by the selective removal of calcium. Phosphate's strong thermophoresis not only achieves its 100-fold up-concentration in aqueous solution, but boosts its solubility by two orders of magnitude. We show that the heat-flow-solubilized phosphate can feed the synthesis of trimetaphosphate, increasing the conversion 260-fold compared to thermal equilibrium. Heat flows thus enhance solubility to unlock apatites as phosphate source for prebiotic chemistry, providing a key to early life's phosphate problem.