Controlling aqueous sorption of humic substances on silica gel by directed alkoxysilyl-derivatization of their functionalities

In this study we explored a possibility for enhancing aqueous sorption of humic substances (HS) onto hydroxylated surfaces (e.g., silica gel) by increasing modification rate of their most abundant functional groups – carboxyls with mineral-adhesive alkoxysilyl moieties. The synthesis included treatment of dried humic material with 3-aminopropyl trimethoxy silane (APTS) capable of forming amide bonds with carboxyl groups of HS under anhydrous conditions. The reaction was run at six different HS to APTS ratio for achieving different modification degrees of the carboxyl groups in the humic backbone. The obtained derivatives were characterized using elemental analysis, 13C NMR Spectroscopy, Fourier transform infrared spectroscopy, and size exclusion chromatography that confirmed quantitative incorporation of alkoxysilyl-moieties into HS structure. Aqueous adsorption was investigated in 0.028 M phosphate buffer using silica gel as a surrogate for mineral surface. Both distribution coefficients as well adsorption capacities paralleled the amount of alkoxysilyl-moieties incorporated into backbone of the parental HS. The adsorption capacity reached its maximum value of 210 mg of HS per g of SiO2 for the APTS derivative synthesized at the equimolar reagent ratio. This value was comparable to the amount of the same HS immobilized onto the APTS-treated silica gel (265 mg of HS per g of SiO2). Adsorption of alkoxysilyl-derivatives was found to be irreversible under conditions studied. Conclusively, we believe that the directed modification of HS by incorporating alkoxysilyl-moieties is well suited for producing humic derivatives with controllable affinity for aqueous sorption onto hydroxylated surfaces.