Adsorption of tetracycline (TC) onto montmorillonite: Cations and humic acid effects

Abstract

The adsorption of tetracycline (TC) on a Na-montmorillonite was studied as a function of five background electrolyte cations (Li+, Na+, K+, Mg2+ and Ca2+), one transitional metal cation (Cu2+) and humic acid (HA) over a pH range from 3 to 9 using batch experiments combined with XRD and FTIR measurement. Results showed that pH had great effect on the TC adsorption and acidic condition is more favored. Monovalent (Li+, Na+ and K+) and divalent (Mg2+, Ca2+ and Cu2+) cations showed very different effects on the TC adsorption onto montmorillonite. In the presence of monovalent cations, the adsorption edge curves were little affected by the types of cations. They presented a great decrease at pH<6, then an increase to a local maximum at about pH 8, followed by a gradual decrease (8<pH<9), which might resulted from cation exchange at the interlayer surface sites and surface complexation at the basal or edge sites. In the presence of divalent cations, the adsorption of TC was enhanced compared to the ones in the presence of monovalent cations, indicating other mechanism might involve. The enhanced TC adsorption has an order: Cu2+≫Ca2+>Mg2+, which might be due to the capability of “bridge” effect of divalent cations. The difference of enhancing TC adsorption in the presence of Ca2+ and Mg2+ might be a result of different ionic radii and different interacting groups in TC molecular. XRD results showed that TC was intercalated into interlayers of montmorillonite since the interlayer expansion was observed. The band changes of amide carbonyl and amino groups in tricarbonyl methane group and the carbonyl group in phenolic deketone group in the FTIR spectra of TC equilibrated with montmorillonite confirmed that TC was adsorbed to the clay via cation exchange and surface complexation. It was also found that the effect of HA on the TC adsorption was pH-dependent and the presence of HA significantly reduced the mobility of TC in solution especially under acidic condition due to the complexation between cationic or zwitterionic TC species and the deprotonated sites on HA (mainly carboxylic groups) via electrostatic attraction. These results suggested that coexistence of divalent cations and HA would reduce TC's mobility in soil environment, especially at acidic condition.