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Adsorption of tetracycline (TC) on kaolinite and montmorillonite was investigated using batch adsorption experiments with different pH, ionic strength, and surface coverage. As a result, pH and ionic strength-dependent adsorption of TC was observed for the two clay minerals. The adsorption of TC decreased with the increase of pH and ionic strength, and high initial TC concentration had high adsorption. In addition, a triple-layer model was used to predict the adsorption and surface speciation of TC on the two minerals. As a result, four complex species on kaolinite (≡X(-)∙H3TC(+), ≡X(-)∙H2TC(±), ≡SOH(0)∙H2TC(±), and ≡SOH(0)∙HTC(-)) and three species on montmorillonite (≡X(-)∙H3TC(+), ≡X(-)∙H2TC(±), and ≡SOH(0)∙HTC(-)) were structurally constrained by spectroscopy, and these species were also successfully fitted to the adsorption edges of TC. Three functional groups of TC were involved in these adsorption reactions, including the positively charged dimethylamino group, the C=O amide I group, and the C=O group at the C ring. Combining adsorption experiments and model in this study, the adsorption of TC on kaolinite and montmorillonite was mainly attributed to cation exchange on the surface sites (≡X(-)) compared to surface complexation on the edge sites (≡SOH) at natural soil pH condition. Moreover, the surface adsorption species, the corresponding adsorption modes, and the binding constants for the surface reactions were also estimated.

Co-contamination of antibiotic and heavy metals commonly occurs in the environment. Tetracycline (TC), a common antibiotic, can behave as an efficient organic ligand to complex with cations. In this paper, the joint toxicity of TC with two commonly existing metals, copper(II) and cadmium(II), towards a luminescent bacteria, Vibrio fischeri, are investigated. Results showed that coexistence of TC and Cu(II) showed a significant antagonistic effect, while TC and Cd(II) showed a synergistic effect. The aqueous speciation of TC with two metal cations was calculated using a chemical equilibrium software Visual MINTEQ and results indicated that a strong complexation exist between TC and Cu(II), while much weaker interaction between TC and Cd(II). Traditional joint toxicity prediction model based on independent action failed to predict the combined toxicity of TC with metals. A new method based on speciation calculation was used to evaluate the joint toxicity of ligands and cations. It is assumed that the metal-ligand complexes are non-toxic to V. fischeri and the joint toxicity is determined by the sum of toxic unit of free metal-ions and free organic ligands. It explained the joint toxicity of the mixed systems reasonably well. Meanwhile, citric acid (CA) and fulvic acid (FA) were also introduced in this study to provide a benchmark comparison with TC. Results showed it is also valid for mixed systems of CA and FA with metals except for the Cd-CA mixture.

The surface adsorption behavior of tetracycline (TC), a zwitterionic antibiotic, to goethite was investigated as a function of pH, ionic strength and TC concentration using batch adsorption experiments and structural information was derived from attenuated total reflectance Fourier transform infrared spectrum observations. The spectroscopic results suggested that the tricarbonylamide group and the phenolic diketone group of the TC molecule were involved in interacting with the goethite surface depending on the pH level. A charge distribution surface complexation model was developed to describe the macroscopic adsorption trends. Two inner-sphere surface complexation species could successfully describe observed adsorption trends: under acidic condition TC may interact with the surface of goethite, forming a monodentate complex through the tricarbonylamide group, while under alkaline condition forming a more stable bidentate complex via the tricarbonylamide and phenolic diketone groups. The model could well predict the adsorption behavior of TC under a relatively wide range of pH, ionic strength and surface coverage. However, since the model did not fully consider the molecular size of TC, the model might overestimate the adsorption when TC surface coverage is higher than 1.42 μmol m(-2)., (© 2013. Published by Elsevier B.V. All rights reserved.)

Tetracycline (TC), a common antibiotic, can behave as an efficient ligand with cations, but the effect of its interaction with heavy metal cations on the mobility of both species in soils has not been well evaluated. In this study, the complexation affinities of TC with Cd (II), Cu (II) and Pb (II) were examined using potentiometric titration and spectroscopic methods. The cosorption behavior of TC and metal ions onto three selected Chinese soils was evaluated using batch adsorption experiments. The presence of metal cations promoted TC adsorption through an ion bridging effect in the order Cu (II) > Pb (II) > Cd (II), which is in accordance with their complexation ability with TC. The addition of TC affects metal adsorption differently depending on the solution pH and metal type. Therefore, it is necessary to consider the complexation ability of TC and divalent metal cations when evaluating their mobility in soils., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Adsorption of tetracycline, one of the most widely used antibiotics, onto goethite was studied as a function of pH, metal cations, and humic acid (HA) over a pH range 3-10. Five background electrolyte cations (Li(+), Na(+), K(+), Ca(2+), and Mg(2+)) with a concentration of 0.01 M showed little effect on the tetracycline adsorption at the studied pH range. While the divalent heavy metal cation, Cu(2+), could significantly enhance the adsorption and higher concentration of Cu(2+), stronger adsorption was found. The results indicated that different adsorption mechanisms might be involved for the two types of cations. Background electrolyte cations hardly interfere with the interaction between tetracycline and goethite surfaces because they only form weak outer-sphere surface complexes. On the contrary, Cu(2+) could enhance the adsorption via acting as a bridge ion to form goethite-Cu(2+)-tetracycline surface complex because Cu(2+) could form strong and specific inner-sphere surface complexes. HA showed different effect on the tetracycline sorption under different pH condition. The presence of HA increased tetracycline sorption dramatically under acidic condition. Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Contamination of environmental matrixes by human and animal wastes containing antibiotics is a growing health concern. Because tetracycline is one of the most widely-used antibiotics in the world, it is important to understand the factors that influence its mobility in soils. This study investigated the effects of pH, background electrolyte cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), heavy metal Cu(2+) and humic acid (HA) on tetracycline adsorption onto kaolinite. Results showed that tetracycline was greatly adsorbed by kaolinite over pH 3-6, then decreased with the increase of pH, indicating that tetracycline adsorption mainly through ion exchange of cations species and complexation of zwitterions species. In the presence of five types of cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), tetracycline adsorption decreased in accordance with the increasing of atomic radius and valence of metal cations, which suggested that outer-sphere complexes formed between tetracycline and kaolinite, and the existence of competitor ions lead to the decreasing adsorption. The presence of Cu(2+) greatly enhanced the adsorption probably by acting as a bridge ion between tetracycline species and the edge sites of kaolinite. HA also showed a major effect on the adsorption: at pH < 6, the presence of HA increased the adsorption, while the addition of HA showed little effect on tetracycline adsorption at higher pH. The soil environmental conditions, like pH, metal cations and soil organic matter, strongly influence the adsorption behavior of tetracycline onto kaolinite and need to be considered when assessing the environmental toxicity of tetracycline.

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 (8Mg2+, 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. [Copyright &y& Elsevier]