Complexation of the antibiotic tetracycline with humic acid.

The effect of solution chemistry and sorbate-to-sorbent ratio on the interaction of the antibiotic tetracycline with Elliott soil humic acid (ESHA) was investigated using equilibrium dialysis and FITEQL modeling. Tetracycline speciation strongly influenced its sorption to ESHA. Sorption was strongly pH-dependent with a maximum around pH 4.3, and competition with H+ and electrolyte cation (Na+) was evident. The pH-dependent trend was consistent with complexation between the cationic/zwitterionic tetracycline species and deprotonated sites in ESHA (mainly carboxylic functional groups). Modification of ESHA by Ca2+ addition increased tetracycline sorption suggesting that ternary complex formation (ESHA-metal-tetracycline) may be important at higher concentrations of multivalent metal cations. The macroscopic data (pH-envelope and sorption isotherms) were successfully modeled using a discrete logK function with the FITEQL 4.0 chemical equilibrium program indicating that ESHA-tetracycline interaction could be reasonably represented as complex formation of a monoacid with discrete sites in humic acid. Sorption-desorption hysteresis was observed; both sorption and desorption isotherms were well described by the Freundlich equation.

[1]  W. Stigelman,et al.  Goodman and Gilman's the Pharmacological Basis of Therapeutics , 1986 .

[2]  J. McCarthy,et al.  Subsurface transport of contaminants , 1989 .

[3]  L. Martin-Neto,et al.  Hydrophobic interactions between spin-label 5-SASL and humic acid as revealed by ESR spectroscopy. , 2001, Environmental Science and Technology.

[4]  M. Essington.  Soil and water chemistry , 2003 .

[5]  B. Xing,et al.  Sorption and desorption of naphthalene by soil organic matter: importance of aromatic and aliphatic components. , 2003, Journal of environmental quality.

[6]  L. Goodman,et al.  The Pharmacological Basis of Therapeutics , 1976 .

[7]  P. Hatcher,et al.  Quinoline sorption on kaolinite-humic acid complexes , 1999 .

[8]  L. Krutz,et al.  Adsorption and desorption of metolachlor and metolachlor metabolites in vegetated filter strip and cultivated soil. , 2004, Journal of environmental quality.

[9]  Cheng Gu,et al.  Interaction of tetracycline with aluminum and iron hydrous oxides. , 2005, Environmental science & technology.

[10]  E. Thurman,et al.  Use of radioimmunoassay as a screen for antibiotics in confined animal feeding operations and confirmation by liquid chromatography/mass spectrometry. , 2000, The Science of the total environment.

[11]  J. Pignatello,et al.  An isotope exchange technique to assess mechanisms of sorption hysteresis applied to naphthalene in kerogenous organic matter. , 2005, Environmental science & technology.

[12]  R. Schwarzenbach,et al.  Association of Triorganotin Compounds with Dissolved Humic Acids , 1998 .

[13]  E. Perdue,et al.  Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matter , 2003 .

[14]  J. Lead,et al.  Determination of Diffusion Coefficients of Humic Substances by Fluorescence Correlation Spectroscopy: Role of Solution Conditions , 2000 .

[15]  Jun Ma,et al.  AFM study on the sorbed NOM and its fractions isolated from River Songhua. , 2006, Water research.

[16]  J. McCarthy,et al.  ES&T Features: Subsurface transport of contaminants , 1989 .

[17]  R. Engebretson,et al.  Micro-organization in dissolved humic acids. , 1994, Environmental science & technology.

[18]  K. Karthikeyan,et al.  Humic acid complexation of basic and neutral polycyclic aromatic compounds. , 2002, Chemosphere.

[19]  J. McCarthy,et al.  Interactions between polycyclic aromatic hydrocarbons and dissolved humic material: binding and dissociation. , 1985, Environmental science & technology.

[20]  H. Nau,et al.  Determination of persistent tetracycline residues in soil fertilized with liquid manure by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry. , 2002, Analytical chemistry.

[21]  Diana S Aga,et al.  Simultaneous analysis of multiple classes of antibiotics by ion trap LC/MS/MS for assessing surface water and groundwater contamination. , 2005, Analytical chemistry.

[22]  L. Burkhard,et al.  Estimating Dissolved Organic Carbon Partition Coefficients for Nonionic Organic Chemicals , 2000 .

[23]  Siegfried Schneider,et al.  Spectroscopic investigation of complexation between various tetracyclines and Mg2+ or Ca2+ , 2000 .

[24]  R. Schwarzenbach,et al.  Environmental Organic Chemistry , 1993 .

[25]  E. Thurman,et al.  Analysis of trace levels of sulfonamide and tetracycline antimicrobials in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry. , 2001, Analytical chemistry.

[26]  Diana S Aga,et al.  Investigating the molecular interactions of oxytetracycline in clay and organic matter: insights on factors affecting its mobility in soil. , 2004, Environmental science & technology.

[27]  Jigang Wu,et al.  Interactions of chlorpyrifos with colloidal materials in aqueous systems. , 2004, Journal of environmental quality.

[28]  Johanna Buschmann,et al.  Antimony(III) binding to humic substances: influence of pH and type of humic acid. , 2004, Environmental science & technology.

[29]  E. Thurman,et al.  Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: a national reconnaissance. , 2002 .

[30]  C. Seybold,et al.  Adsorption and Desorption of Atrazine, Deethylatrazine, Deisopropylatrazine, and Hydroxyatrazine on Levy Wetland Soil , 1996 .

[31]  Weilin Huang,et al.  Hysteresis in the sorption and desorption of hydrophobic organic contaminants by soils and sediments: 1. A comparative analysis of experimental protocols , 1998 .

[32]  C. Carter,et al.  Binding of DDT to dissolved humic materials. , 1982, Environmental science & technology.

[33]  M. C. Hermosín,et al.  Sorption and desorption of triadimefon by soils and model soil colloids. , 1999, Journal of agricultural and food chemistry.

[34]  Bent Halling-Sørensen,et al.  Simultaneous extraction of tetracycline, macrolide and sulfonamide antibiotics from agricultural soils using pressurised liquid extraction, followed by solid-phase extraction and liquid chromatography-tandem mass spectrometry. , 2004, Journal of chromatography. A.

[35]  A. MacKay,et al.  Sorption of oxytetracycline to iron oxides and iron oxide-rich soils. , 2005, Environmental science & technology.

[36]  R. Mackie,et al.  Occurrence and Diversity of Tetracycline Resistance Genes in Lagoons and Groundwater Underlying Two Swine Production Facilities , 2001, Applied and Environmental Microbiology.

[37]  J Tolls,et al.  Sorption of veterinary pharmaceuticals in soils: a review. , 2001, Environmental science & technology.

[38]  A. MacKay,et al.  Modeling tetracycline antibiotic sorption to clays. , 2004, Environmental science & technology.

[39]  J. Zachara,et al.  Interaction of hydrophobic organic compounds with mineral-bound humic substances. , 1994, Environmental science & technology.

[40]  Sören Thiele-Bruhn,et al.  Pharmaceutical antibiotic compounds in soils – a review , 2003 .

[41]  A. MacKay,et al.  Oxytetracycline sorption to organic matter by metal-bridging. , 2005, Journal of environmental quality.

[42]  K. Karthikeyan,et al.  Occurrence of antibiotics in wastewater treatment facilities in Wisconsin, USA. , 2006, The Science of the total environment.

[43]  R. Wandruszka,et al.  Effects of pH and Metals on the Surface Tension of Aqueous Humic Materials , 1999 .

[44]  W. E. Ford,et al.  The Complexation of Tetracycline and Anhydrotetracycline with Mg2+ and Ca2+: A Spectroscopic Study , 1998 .

[45]  K. Karthikeyan,et al.  Effects of solution chemistry on the oxidative transformation of 1-naphthol and its complexation with humic acid , 2000 .

[46]  G. D. Turner,et al.  Models for Association of Metal Ions with Heterogeneous Environmental Sorbents. 1. Complexation of Co(II) by Leonardite Humic Acid as a Function of pH and NaClO4 Concentration. , 1995, Environmental science & technology.

[47]  James J. Morgan,et al.  Effects of aqueous chemistry on the binding of polycyclic aromatic hydrocarbons by dissolved humic materials , 1993 .

[48]  R. Guy,et al.  Models for tetracycline in aquatic environments , 1987 .

[49]  G. Sposito,et al.  Molecular structure in soil humic substances: the new view. , 2005, Environmental science & technology.

[50]  C. Vaz,et al.  Sorption interactions between imazaquin and a humic acid extracted from a typical Brazilian oxisol. , 2002, Journal of environmental quality.