Fast removal of aqueous Hg(ii) with quaternary ammonium-functionalized magnetic mesoporous silica and silica regeneration

Humic acid (HA) coated Fe3O4 nanoparticles (Fe3O4/HA) were developed for the removal of toxic Hg(II), Pb(II), Cd(II), and Cu(II) from water. Fe3O4/HA were prepared by a coprecipitation procedure with cheap and environmentally friendly iron salts and HA. TOC and XPS analysis showed the as-prepared Fe3O4/HA contains approximately 11% (w/w) of HA which are fractions abundant in O and N-based functional groups. TEM images and laser particle size analysis revealed the Fe3O4/HA (with approximately 10 nm Fe3O4 cores) aggregated in aqueous suspensions to form aggregates with an average hydrodynamic size of approximately 140 nm. With a saturation magnetization of 79.6 emu/g, the Fe3O4/HA can be simply recovered from water with magnetic separations at low magnetic field gradients within a few minutes. Sorption of the heavy metals to Fe3O4/HA reached equilibrium in less than 15 min, and agreed well to the Langmuir adsorption model with maximum adsorption capacities from 46.3 to 97.7 mg/g. The Fe3O4/HA was stable in tap water, natural waters, and acidic/ basic solutions ranging from 0.1 M HCl to 2 M NaOH with low leaching of Fe (< or = 3.7%) and HA (< or = 5.3%). The Fe3O4/HA was able to remove over 99% of Hg(ll) and Pb(ll) and over 95% of Cu(II) and Cd(II) in natural and tap water at optimized pH. Leaching back of the Fe3O4/HA sorbed heavy metals in water was found to be negligible.

We have shown that superparamagnetic iron oxide (Fe3O4) nanoparticles with a surface functionalization of dimercaptosuccinic acid (DMSA) are an effective sorbent material for toxic soft metals such as Hg, Ag, Pb, Cd, and Tl, which effectively bind to the DMSA ligands and for As, which binds to the iron oxide lattices. The nanoparticles are highly dispersible and stable in solutions, have a large surface area (114 m2/g), and have a high functional group content (1.8 mmol thiols/g). They are attracted to a magnetic field and can be separated from solution within a minute with a 1.2 T magnet. The chemical affinity, capacity, kinetics, and stability of the magnetic nanoparticles were compared to those of conventional resin based sorbents (GT-73), activated carbon, and nanoporous silica (SAMMS) of similar surface chemistries in river water, groundwater, seawater, and human blood and plasma. DMSA-Fe3O4 had a capacity of 227 mg of Hg/g, a 30-fold larger value than GT-73. The nanoparticles removed 99 wt% of 1 mg/L Pb within a minute, while it took over 10 and 120 min for Chelex-100 and GT-73 to remove 96% of Pb.