Composition and binding properties of THFA were studied by 2D-COS-FTIR and NMR. Higher N content and lower C/N ratio were observed in the non-bloom FA. N-rich organic compounds in non-bloom FA showed faster binding sequence to Cu(II). Carboxyl groups in bloom FA evidenced the fastest responses to Cu(II) binding. Algal products and microbial metabolism altered the binding process of FA-Cu(II).