Charge transfer between benzene-1,3-diamidoethanethiol (BDET) and metal sulfides affect efficiency of acid mine drainage treatment

Acid mine drainage (AMD) from metal sulfides that result in heavy metal leaching into the environment is a prevalent problem. Coating natural pyrite (FeS2/SiO2) and galena (PbS) mineral surfaces with benzene-1,3-diamidoethanethiol (BDET) was found to be an effective method for preventing heavy metal leaching into aqueous media. The natural pyrite examined was found to have a significant amount of quartz in its matrix that influenced its ability to bind with BDET. X-ray photoelectron spectroscopy (XPS) core level shifts of the S 2p, N1s, Fe 2p and Pb 4f orbitals upon complexation revealed that greater BDET binding to these metal sulfides correlated with ligand-to-metal (LMCT) charge transfer. Improved binding of BDET to FeS2 over PbS was observed as the concentration of metal in the supernatant dramatically decreased. Stronger BDET binding to FeS2/SiO2 was attributed to LMCT from the open shell Fe absent in the corresponding metal in galena (Pb), which had a closed shell configuration. Comparison of N 1s spectra in control experiments show that SiO2 resulted in a reduced number of N 1s oxidation states, improving anti-leaching properties. Coverage of BDET complexed to FeS2/SiO2 was markedly greater than that for PbS, in agreement with inductive coupled plasma optical emission spectrometry (ICP-OES) data. Photoelectron spectroscopy data revealed that the electronic shell structure of the sulfide metal is a contributing factor in BDET’s ability to inhibit heavy metal leaching.