Hypothesis: Hydroxamate and sulfhydryl surfactants are effective collectors for flotation of copper minerals. The combination application of hydroxamate and sulfhydryl collectors has been proved to be an effective approach for improving the flotation recovery of non-sulfide copper minerals. A surfactant owing both hydroxamate and dithiocarbamate groups might exhibit strong affinity to non-sulfide copper minerals through double sites adsorption, rendering an enhanced hydrophobization to non-sulfide copper minerals flotation. Experiments: The flotation performance of S-[(2-hydroxyamino)-2-oxoethyl]- N,N-dibutyldithiocarbamate (HABTC) to malachite, calcite and quartz were first evaluated through systematic micro-flotation experiments. HABTC's hydrophobic mechanism to malachite was further investigated and analyzed by zeta potential, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). Findings: The micro-flotation results demonstrated HABTC was an excellent collector for malachite flotation and exhibited favorable selectivity for flotation separation of malachite from quartz or calcite under pH 8.5-103. Zeta potential and FTIR implied that HABTC might bond with the surface copper atoms of malachite, with releasing the Fr ions of its hydroxamate group into pulp. ToF-SIMS provided clear evidences that the Cu-hydroxamate and Cu-dithiocarbamate groups were formed on malachite surfaces after HABTC adsorption. XPS revealed that Cu(l)/Cu(II) mixed -valence surface complexes of HABTC anchored on malachite through formation of Cu(l) S and Cu(II)-O bonds, accompanying with reduction of partial surface Cu(II) to Cu(I). The Cu(I)/Cu(II) mixed -valence double chelating character and "chair"-shape N,N-dibutyldithiocarbamate hydrophobic group, resulting in an enhanced affinity and hydrophobization of HABTC to malachite flotation. (C) 2017 Elsevier Inc. All rights reserved.