Impact of redox evolution of layered double hydroxides on the immobilisation of structural and adsorbed heavy metals

Abstract In the soil environment, divalent heavy metal ions often interact with trivalent metal ions to form hydrotalcite supergroup nanominerals (also known as natural layered double hydroxides, LDHs), effectively immobilising heavy metals within the minerals structure. Concurrently, these LDH minerals also show high surface reactivity and can adsorb surrounding heavy metal ions, thus they play a significant role in heavy metal pollution purification. However, the impact of the subsequent geochemical evolution of heavy-metal-containing LDHs on the migration and transformation of structural and surface-adsorbed heavy metals as well as its surface reactivity towards surrounding heavy metals remains unclear. Herein, Ni(II)Fe(III)-LDH and Co(II)Al(III)-LDH were taken as examples to reveal the influence of redox evolution on the immobilisation of structural and adsorbed heavy metals. The results of this work indicate that the oxidative–reductive alternating evolution of structural Ni, Fe and Co elements constrain the transformation of heavy metals, as well as their bioavailability greatly. The oxidative–reductive alternating evolution helped reduce the content of bioavailable heavy metals in exchangeable and carbonate-bounded states. It can also enhance the integration of heavy metals with the LDH structure and help transform heavy metals into residual states, thereby reducing their mobility and bioavailability. However, oxidative–reductive evolution significantly reduced the surface reactivity of LDHs, diminishing their interface locking ability for surrounding heavy metal ions. This research provides foundational data for assessing the long-term environmental performance of LDHs.