A least-squares approach has been used to determine multiplicative scaling factors for harmonic vibrational frequencies to facilitate comparison with experimentally observed frequencies. The harmonic frequencies were calculated using several of the most popular quantum chemical methods (HF, MP2, and B3LYP) and the correlation consistent family of basis sets (cc-pVxZ and aug-cc-pVxZ, where x ) D(2), T(3), or Q(4)). Calculations were performed on 41 organic molecules for which fundamental frequencies are well established. When the derived scaling factors are applied, the percentage of calculated frequencies that deviate less than 3% from the experimental frequencies is 93-97% for B3LYP and 88-92% for MP2 when quadruple-ζ level basis sets are used. Similarly, scaling factors were determined for computing the vibrational components of the thermal contributions to enthalpy and entropy. An additional set of molecules was used in calculating scaling factors for the zero-point vibrational energy.

The effect of solution chemistry (pH, sorbate-to-sorbent ratio, ionic strength (/)) and reaction time on the sorption of tetracycline to the hydrous oxides of Al (HAO) and Fe (HFO) was examined. Sorption to HAO increased with increasing pH upto pH 7 (no such trend for HFO) above which it decreased at higher pH values for both the hydrous oxides. Experimental results indicate that ligand-promoted dissolution is occurring during tetracycline sorption to these hydrous oxides. Ligand-promoted dissolution was more significantfor HAO than HFO attributable to the difference in labile surface sites between these two sorbents. The ability of tetracycline to form strong complexes with Al and Fe will increase the solubility of these minerals. Sorption of tetracycline was quite rapid and equilibrium was achieved after 8 h. However, soluble metal (Me: Al or Fe) concentrations attained equilibrium only after 24 h. Ligand-promoted dissolution appears to be a two-step process; initially, 1:1 Me-tetracycline soluble complexes are formed and as the reaction progresses 2:1 complexes existed. Increasing / (from 0.01 to 0.5 M) decreased the sorption extent only at higher sorbate-to-sorbent ratios suggesting the dominance of inner-sphere type complexes at low equilibrium tetracycline concentrations. Spectroscopic evidence indicates that tricarbonylamide and carbonyl functional groups of tetracycline could be responsible for sorption to mineral surfaces. Our research findings will increase understanding of the environmental occurrence, fate, and transport characteristics of antibiotics, which are considered as emerging organic contaminants.

In the environment, microplastics are subjected to multiple aging processes; however, information regarding the impact of aging on the environmental behavior of microplastics is still lacking. This study investigated the alteration properties of polystyrene and high-density polyethylene microplastics by heat-activated K2S2O8 and Fenton treatments to improve the understanding of their long-term natural aging in aquatic environments. Our results indicated that the O/C ratio was an alternative parameter to the carbonyl index (CI) to quantitatively describe the surface alteration properties of microplastics. The correlation model of the O/C ratio or CI versus alteration time was developed and compared by natural alteration of microplastics in freshwater samples. Moreover, the regression equation of the equilibrium adsorption capacity of altered microplastics versus the O/C ratio and average size was proposed. This study is the first effort in differentiating the relationships between the alteration properties and alteration time/adsorption capacity of microplastics, which would be helpful for predicting the weathering degree and accumulation of hydrophilic antibiotics onto aged microplastics in aquatic environments. This research develops promising strategies to accelerate the aging reactions using advanced oxidation processes, which would provide further information to assess the microplastic pollution in actual environments.

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