Liangliang Ji

Significant concerns have been raised over the presence of antibiotics including tetracyclines in aquatic environments. We herein studied single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT) as potential effective adsorbents for removal of tetracycline from aqueous solution. In comparison, a nonpolar adsorbate, naphthalene, and two other carbonaceous adsorbents, pulverized activated carbon (AC) and nonporous graphite, were used. The observed adsorbent-to-solution distribution coefficient (Kd, L/kg) of tetracycline was in the order of 10(4)-10(6) L/kg for SWNT, 10(3)-10(4) L/kg for MWNT, 10(3)-10(4) L/kg for AC, and 10(3)-10(5) L/kg for graphite. Upon normalization for adsorbent surface area, the adsorption affinity of tetracycline decreased in the order of graphite/ SWNT > MWNT >> AC. The weaker adsorption of tetracycline to AC indicates that for bulky adsorbates adsorption affinity is greatly affected by the accessibility of available adsorption sites. The remarkably strong adsorption of tetracycline to the carbon nanotubes and to graphite can be attributed to the strong adsorptive interactions (van der Waals forces, pi-pi electron-donor-acceptor interactions, cation-pi bonding) with the graphene surface. Complexation between tetracycline and model graphene compounds (naphthalene, phenanthrene, pyrene) in solution phase was verified by ring current-induced 1H NMR upfield chemical shifts of tetracycline moieties.

The presence of sulfonamide antibiotics in aquatic environments has been recognized as an issue warranting consideration. In this study, we evaluated multiwalled carbon nanotubes (MWNT) as a potential effective adsorbent for removal of two sulfonamide antibiotics, sulfapyridine and sulfamethoxazole, from aqueous solutions. Nonporous, functionality-free graphite was included as a comparative adsorbent. Despite the very low hydrophobicity, the two sulfonamides adsorbed strongly to MWNT and graphite, a fact attributed to pi-pi electron coupling with the graphene surface of the adsorbent. For both sulfonamide antibiotics, similar patterns of pH-dependent adsorption were observed between MWNT and graphite, implying the predominance of graphene structures for the adsorption to MWNT. Moreover, the observed pH effects on adsorption indicate that the protonated neutral form of sulfonamide adsorbs much more strongly than the deprotonated anionic counterpart does. The effects of ionic strength (NaCl and CaCl2) and the presence of a dissolved soil humic acid on adsorption of the two antibiotics to MWNT and graphite were also assessed. Ring current-induced 1H NMR upfield chemical shifts further verified face-to-face complex formation between neutral sulfamethoxazole and model pi-electron donor compounds (naphthalene, phenanthrene, and pyrene) in solution.

The main objective of this study was to investigate the key factors and mechanisms of antibiotic adsorption on crop residue-derived black carbon, as well as the relative importance of black carbon to the overall sorption to soil. Batch sorption experiments were performed for two reference antibiotics (sulfamethoxazole and tetracycline) on wheat- and maize-residue-derived black carbon. After removal of the mineral fraction from the raw black carbon by acidification, tetracycline exhibited less enhanced adsorption than sulfamethoxazole, implying stronger complexation of tetracycline on the mineral components. The antibiotic adsorption on the demineralized black carbon was very strong (The measured K(d) was in the order of 10(3)-10(5) L/kg). The adsorbent surface area-normalized adsorption of sulfamethoxazole was higher on the demineralized black carbon than on nonporous graphite due to the micropore-filling effect. The opposite trend observed for bulky tetracycline was attributed to the size-exclusion effect. Owing to the strong surface complexation and/or cation exchange reaction, sorption of tetracycline to Na(+)-exchanged montmorillonite, soil humic acids, and bulk soil was remarkably stronger than sulfamethoxazole. It was estimated that the contribution of black carbon to the overall sorption to bulk soil was important for sulfamethoxazole, but negligible for tetracycline.

The presence of pharmaceutical antibiotics in aquatic environments poses potential human health and ecological risks. We synthesized ordered micro- and mesoporous carbons, and further conducted batch experiments to systematically examine their adsorption properties toward three antibiotics, sulfamethoxazole, tetracycline, and tylosin, in aqueous solution. In comparison, nonporous graphite, single-walled carbon nanotubes, and two commercial microporous activated carbons were included as additional adsorbents. Adsorption of low-sized sulfamethoxazole was stronger on the activated carbons than on other carbonaceous adsorbents resulting from the pore-filling effect; in contrast, due to the size-exclusion effect adsorption of bulky tetracycline and tylosin was much lower on the activated carbons, especially for the more microporous one, than on the synthesized carbons. After normalizing for adsorbent surface area, adsorption of tetracycline and tylosin on the synthesized carbons was similar to that on nonporous graphite, reflecting complete accessibility of the adsorbent surface area in adsorption. Additionally, compared with other porous adsorbents the synthesized carbons showed faster adsorption kinetics of tetracycline and tylosin, which was attributed to their regular-shaped, open and interconnected three-dimensional pore structure. The findings indicate that template-synthesized micro- and mesoporous carbons are promising adsorbents for the removal of antibiotics, particularly, the bulky and flexible-structured compounds, from aqueous solution.