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The widespread use of silver nanoparticles (AgNPs) inevitably leads to the environmental release of AgNPs. The released AgNPs can pose ecological risks because of their specific toxicity. However, they can also be used as secondary sources of silver metal. Herein, hierarchical mesoporous calcite (HMC) was prepared and used to remove and recover AgNPs from an aqueous solution. The batch experiments show that the HMC has high removal percentages for polyvinylpyrrolidone- and poly (vinyl alcohol)-coated AgNPs (PVP- and PVA-AgNPs) over a