Hongbo Peng

Adsorption of ofloxacin and norfloxacin on carbon nanotubes: Hydrophobicity- and structure-controlled process

Adsorption of antibiotics on solid particles is a key process controlling their fate in the subsurface. This study compared the adsorption of ofloxacin and norfloxacin (NOR) on carbon nanotubes (CNTs) to evaluate the role of structural and hydrophobic properties in regulating their adsorption. A significant relationship was observed between single-point adsorption coefficients (K(d)) and specific surface area (highly hydrophobic), but not between K(d)s and oxygen content. This result suggested that site-specific adsorption was not important but hydrophobic effect may have an important contribution to OFL and NOR adsorption on CNTs. However, normalizing the adsorption coefficients by OFL and NOR solubilities enlarged their adsorption difference indicating that hydrophobicity was not the only factor controlling the difference between OFL and NOR adsorption on CNTs. Their chemical structures show that both chemicals could interact with CNTs through an electron-donor-acceptor mechanism. This mechanism was correlated with the different adsorption of OFL and NOR on functionalized CNTs (namely hydroxylized, carboxylized, and graphitized CNTs). This study revealed that OFL and NOR adsorption was controlled by their both structural- and hydrophobic-properties.

Adsorption of ofloxacin on carbon nanotubes: Solubility, pH and cosolvent effects

The adsorption of ofloxacin (OFL) on carbon nanotubes (CNTs) has been investigated using the solubility, pH and cocolvent effects. In this work, solubilities of OFL and sorption of OFL on three multi-walled CNTs at different pHs and different methanol volume fractions (f(c)) of methanol/water mixture solutions were systematically measured. The solubilities of different OFL species were obtained based on the analysis of pH-dependent solubility. Cationic and anionic OFL showed much higher solubilities than zwitterionic OFL. The highest sorption was not observed at the pH with lowest OFL solubility, indicating hydrophobic interaction was not the dominant sorption mechanism. The sorption decreasing in pH range of 5-8 was consistent with cationic OFL species distribution, suggesting cation exchange may play an important role. With the increased methanol fraction, both OFL solubility and sorption decreased, which was different from hydrophobic organic contaminants (HOCs). Analysis of methanol-fraction-dependent OFL sorption suggested that cosolvent-sorbent (methanol-CNTs) interactions were much stronger than solute-cosolvent (OFL-methanol) interactions. This statement was also confirmed in sorption isotherm study as evidenced by decreased sorption and increased linearity of the isotherms in methanol than those in water.

Coadsorption of Cu and sulfamethoxazole on hydroxylized and graphitized carbon nanotubes

Because of their various functional groups, antibiotics may complex with heavy metals and thus the environmental behaviors of both antibiotics and heavy metals may be altered. Noticing the experimental flaws of the previous studies, this study used Cu(2+) and sulfamethoxazole (SMX) as model sorbates and carbon nanotubes (CNTs) as model sorbents to investigate the coadsorption of Cu and SMX. Combining the results of binary interaction experiments, we concluded that Cu and SMX preferentially occupy different types of CNT sorption sites at pHs 1.0 and 3.5, showing no apparent sorption change with the presence of coadsorbates. However, at pH 6.5, ternary complexes of Cu-SMX-CNTs and SMX-Cu-CNTs may be formed depending on Cu(2+) concentrations. XPS data provided further support for the adsorption of both Cu and SMX on CNTs. These results indicated that the environmental behavior of antibiotics should be evaluated with careful consideration of the rule of metal ions.

The opposite impacts of Cu and Mg cations on dissolved organic matter-ofloxacin interaction.

Dialysis equilibrium system was applied to investigate the roles of Cu(II) and Mg(II) on DOM-ofloxacin (OFL) interaction. The binding behavior of both cations and OFL were studied. The introduction of Cu(II) increased DOM-OFL interaction, while Mg(II) decreased DOM-OFL binding. Cu(II) binding to DOM was also increased by OFL, while Mg(II) binding was decreased by OFL. The change in OFL binding amount in the absence and presence of cations (ΔC(b)) was calculated and compared with cation binding (C(b)(m)). ΔC(b)/C(b)(m) was in the range of 1-3 for Cu(II) depending on the applied Cu concentration. Two ternary complexes of DOM-OFL-Cu and DOM-Cu-OFL were proposed. For Mg(II), ΔC(b)/C(b)(m) was around -1 at Mg(II) concentrations lower than 1 mM, but decreased up to -5 with increasing Mg(II) concentration. The competitive effect of Mg(II) to OFL was thus proposed. FTIR spectra were collected for mechanistic discussion.

Cosorption of organic chemicals with different properties: Their shared and different sorption sites

Complementary sorption of different chemicals was expected and investigating the relationship between the sorption inhibition of primary sorbate (ΔQ(pri)) and sorption of secondary sorbate (Q(sec)) could provide a new angle to understand coadsorption of different chemicals. This study used bisphenol A (BPA) as the primary adsorbate, sulfamethoxazole (SMX) as the competitor, and carbon nanotubes as model adsorbents to study their complementary and competitive adsorption. At low BPA concentrations, the sorption of SMX (Q(sec)) exceeded BPA sorption inhibition (ΔQ(pri)), indicating that these two chemicals complementarily adsorbed on their respectively preferred sorption sites. At high BPA concentrations, higher ΔQ(pri) was observed in comparison to Q(sec), which may be resulted from different packing efficiencies of the adsorbed SMX and BPA. This study emphasized that both competitive and complementary sorption should be discussed in binary sorption system.

Co-sorption of ofloxacin and Cu(II) in soils before and after organic matter removal

Various mechanisms play roles simultaneously for antibiotic sorption on solid particles. Previous studies simply emphasized mechanisms that match the increased or decreased antibiotic sorption by metal ions, without a general concept including these diverse mechanisms in their co-sorption. We observed both increased and decreased OFL and Cu(II) sorption in their co-sorption system. The comparison of the sorption coefficients of primary adsorbate (Kd(pri)) and co-adsorbate (Kd(co)) suggested that enhanced sorption occurred at high Kd(pri) region (low primary adsorbate concentration). Competitive sorption was observed when Kd(pri) was decreased to a certain value depending on solid particle properties. We thus summarized that if the adsorbates were introduced with low concentrations, OFL (such as hydrophobic region in solid particles) and Cu(II) (such as inner-sphere complexation sites) occupied their unique high-energy sorption sites. Cu(II) complexed with the adsorbed OFL, and OFL bridged by the adsorbed Cu(II) promoted the sorption for both chemicals. With the increased concentrations, the adsorbates spread to some common sorption sites with low sorption energy, such as cation exchange and electrostatic attraction region. The overlapping of Cu(II) and OFL on these sorption sites resulted in competitive sorption at high concentrations. The previously reported apparently increased or decreased sorption in antibiotic-metal ion co-sorption system may be only a part of the whole picture. Extended study on the turning point of decreased and increased sorption relating to water chemistry conditions and solid particle properties will provide more useful information to predict antibiotic-metal ion co-sorption.

Contribution of coated humic acids calculated through their surface coverage on nano iron oxides for ofloxacin and norfloxacin sorption

Sorption of organic contaminants on organo-mineral complexes has been investigated extensively, but the sorption contribution of mineral particles was not properly addressed before calculating KOC, especially for ionic organic contaminants. We measured the surface coverage of a humic acid (HA) on nano iron oxides (n-Fe2O3) in a series of synthesized organo-mineral complexes. The contribution of the coated HA to ofloxacin (OFL) and norfloxacin (NOR) sorption in HA-n-Fe2O3 complexes was over 80% of the total sorption with the surface coverage of 36% and fOC of 1.6%. All the coated HA showed higher sorption to NOR and OFL in comparison to the original HA, suggesting HA fractionation and/or physical re-conformation during organo-mineral complex formation. The decreased KOC with multilayer coating may suggest the importance of site-specific interactions for OFL sorption, while the increased KOC with multilayer coating may suggest the importance of partitioning in hydrophobic region for NOR sorption.

Sorption comparison between phenanthrene and its degradation intermediates, 9,10-phenanthrenequinone and 9-phenanthrol in soils/sediments

The degradation intermediates of phenanthrene (PHE) may have increased health risks to organisms than PHE. Therefore, environmental fate and risk assessment studies should take into considerations of PHE degradation products. This study compared the sorption properties of PHE and its degradation intermediates, 9,10-phenanthrenequinone (PQN) and 9-phenanthrol (PTR) in soils, sediments and soil components. A relationship between organic carbon content (f(OC)) and single-point sorption coefficient (logK(d)) was observed for all three chemicals in 10 soils/sediments. The large intercept in the logf(OC)-logK(d) regression for PTR indicated that inorganic fractions control PTR sorption in soils/sediments. No relationship between specific surface area and K(d) was observed. This result indicated that determination of surface area based on gas sorption could not identify surface properties for PHE, PQN, and PTR sorption and thus provide limit information on sorption mechanisms. The high sorption and strong nonlinearity (low n values) of PTR in comparison to PHE suggested that the mobility of PTR could be lower than PHE. Increased mobility of PQN compared with PHE may be expected in soils/sediments because of PQN lower sorption. The varied sorption properties of the three chemicals suggested that their environmental risks should be assessed differently.

Sorption and solubility of ofloxacin and norfloxacin in water-methanol cosolvent.

Prediction of the properties and behavior of antibiotics is important for their risk assessment and pollution control. Theoretical calculation was incorporated in our experimental study to investigate the sorption of ofloxacin (OFL) and norfloxacin (NOR) on carbon nanotubes and their solubilities in water, methanol, and their mixture. Sorption for OFL and NOR decreased as methanol volume fractions (fc) increased. But the log-linear cosolvency model could not be applied as a general model to describe the cosolvent effect on OFL and NOR sorption. We computed the bond lengths of possible hydrogen bonds between solute and solvent and the corresponding interaction energies using Density Functional Theory. The decreased OFL solubility with increased fc could be attributed to the generally stronger hydrogen bond between OFL and H2O than that between OFL and CH3OH. Solubility of NOR varied nonmonotonically with increasing fc, which may be understood from the stronger hydrogen bond of NOR-CH3OH than NOR-H2O at two important sites (-O18 and -O21). The interaction energies were also calculated for the solute surrounded by solvent molecules at all the possible hydrogen bond sites, but it did not match the solubility variations with fc for both chemicals. The difference between the simulated and real systems was discussed. Similar sorption but different solubility of NOR and OFL from water-methanol cosolvent suggested that sorbate-solvent interaction seems not control their sorption.

Temperature dependence of ofloxacin fluorescence quenching and complexation by Cu(II).

The coexistence of heavy metals and antibiotics is common in the environment, and their interactions may mutually alter their environmental behaviors and risks. This study investigated ofloxacin (OFL)-Cu(II) interaction using fluorescence quenching experiments. The possible artifacts were excluded and OFL quenching was attributed to static quenching as suggested by the linear Stern-Volmer plot and decreased quenching with increased temperature. The OFL-Cu(II) interaction was quantitatively described using a stoichiometry equation. The calculation suggested that OFL-Cu(II) association was the mixture of 1:1 and 1:2 complexes. The negative ΔG values and the negative ΔH values suggested that the complexation is a spontaneous and exothermic process. Cation-π binding and electrostatic interaction were excluded and the complexation of Cu(II) with OFL ketonic and carboxyl groups was proposed through UV-visible spectrum characterization, pH dependent complexation, and thermodynamic analysis.