)DWHRI 3KDUPDFHXWLFDOV LQWKH (QYLURQPHQW DQGLQ :DWHU7UHDWPHQW 6\VWHPV © 2008 by Taylor & Francis Group, LLC )DWHRI 3KDUPDFHXWLFDOV LQWKH (QYLURQPHQW DQGLQ :DWHU7UHDWPHQW 6\VWHPV Edited by Diana S. Aga CRC Press is an imprint of the Taylor & Francis Group, an informa business Boca Raton London New York © 2008 by Taylor & Francis Group, LLC CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2008 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-13: 978-1-4200-5232-9 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. 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For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Fate of pharmaceuticals in the environment and in water treatment systems / edited by Diana S. Aga. p. cm. Includes bibliographical references and index. ISBN 978-1-4200-5232-9 (alk. paper) 1. Drugs Environmental aspects. 2. Water Pollution. 3. Water Purification. I. Aga, Diana S., 1967- II. Title. TD196.D78F38 2008 628.5’2 dc22 2007029935 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com © 2008 by Taylor & Francis Group, LLC v Contents Preface vii Editor ix Contributors xi PART I Occurrence and Analysis of Pharmaceuticals in the Environment Chapter 1 Environmental Presence and Persistence of Pharmaceuticals: An Overview 3 Susan T. Glassmeyer, Dana W. Kolpin, Edward T. Furlong, and Michael J. Focazio Chapter 2 Advances in the Analysis of Pharmaceuticals in the Aquatic Environment 53 Sandra Pérez and Damià Barceló Chapter 3 Sample Preparation and Analysis of Solid-Bound Pharmaceuticals 81 Christine Klein, Seamus O’Connor, Jonas Locke, and Diana Aga Chapter 4 Gadolinium Containing Contrast Agents for Magnetic Resonance Imaging (MRI): Investigations on the Environmental Fate and Effects 101 Claudia Neubert, Reinhard Länge, and Thomas Steger-Hartmann PART II Environmental Fate and Transformations of Veterinary Pharmaceuticals Chapter 5 Fate and Transport of Veterinary Medicines in the Soil Environment 123 Alistair B.A. Boxall Chapter 6 Sorption and Degradation of Selected Pharmaceuticals in Soil and Manure 139 Nadia Carmosini and Linda S. Lee © 2008 by Taylor & Francis Group, LLC vi Fate of Pharmaceuticals in the Environment and in Water Treatment Systems Chapter 7 Mobility of Tylosin and Enteric Bacteria in Soil Columns 167 Keri L. Henderson,Thomas B. Moorman, and Joel R. Coats Chapter 8 Plant Uptake of Pharmaceuticals from Soil: Determined by E LISA 179 Rudolf J. Schneider Chapter 9 AntibioticTransformationinPlantsviaGlutathione Conjugation 199 Michael H. Farkas, James O. Berry, and Diana S. Aga PART III Treatment of Pharmaceuticals in Drinking Water and Wastewater Chapter 10 Drugs in Drinking Water: Treatment Options 217 Howard S. Weinberg, Vanessa J. Pereira, and Zhengqi Ye Chapter 11 Removal of Endocrine Disruptors and Pharmaceuticals during Water Treatment 229 Shane A. Snyder, Hongxia Lei, and Eric C. Wert Chapter 12 ReactionandTransformationofAntibacterialAgentswith Aqueous Chlorine under Relevant Water Treatment Conditions 261 Ching-Hua Huang, Michael C. Dodd, and Amisha D. Shah Chapter 13 Hormones in Waste from Concentrated Animal Feeding Operations 291 Z. Zhao, K.F. Knowlton, and N.G. Love Chapter 14 Treatment of Antibiotics in Swine Wastewater 331 Craig D. Adams Chapter 15 Removal of Pharmaceuticals in Biological Wastewater Treatment Pla nts 349 Sungpyo Kim, A. Scott Weber, Angela Batt, and Diana S. Aga Chapter 16 Chemical Processes dur ing Biological Wastewater Treatment 363 Willie F. Harper, Jr., Tamara Floyd-Smith, and Taewoo Yi © 2008 by Taylor & Francis Group, LLC vii Preface Recentadvancesinanalyticalinstrumentationhavebeenmirroredbyourincreased abilitytodetectandquantifyorganiccontaminantsattracelevels,eveninhighly complexmatricessuchaswastewater,manure,andsoil.Incontrasttothehydro- phobicpersistentorganicpollutants(forexample,PCBs,DDT)thatareoftenfound in the environment at parts-per-million or parts-per-billion concentrations, pharma- ceutical compounds are generally present at the parts-per-trillion or low parts-per- billion range and are mostly polar. Consequently, the detection of pharmaceutical residues in the environment remained elusive until modern instruments such as liq- uid chromatography/mass spectrometry (LC/MS) became commonplace in many environmental laboratories. As a result, many scientists have now documented the occurrence of residues of pharmaceuticals and personal-care products, which have been termed “emerging contaminants” in various environmental compartments. Questionsregardingpersistenceandlong-termadverseeffectsofpharmaceuticals in the environment have been raised because there have been reports that very low drug concentrations (for example, ng/L) in the environment can have undesirable ecological and potentially human health effects. The rst section of this book, “Occurrence and Analysis of Pharmaceuticals in the Environment,” includes a chapter prepared by leading researchers from the U.S. EnvironmentalProtectionAgencyandtheU.S.GeologicalSurvey,whichprovides an overview of the momentous publications that have been instrumental in the recog- nition of emerging contaminants. A compilation of the most current (2004 through 2006) literature on the presence and concentrations of pharmaceuticals in the envi- ronment is also presented. This information is complemented by the subsequent review chapters on the recent advances in instrumentation and sample preparation techniquesinenvironmentalanalysisthathaveplayedacriticalroleintheadvance- ment of our knowledge on the environmental fate of pharmaceuticals. Finally, an example of how risk assessment is conducted to investigate the fate and effects of pharmaceutical contaminants is included in this rst section. Animportantsourceofpharmaceuticalcontaminantsisthroughlandapplica- tion of livestock manure to fertilize crops. Many animal operations generate manure thatcontainsantibioticssinceanimalsreceivethesedrugsinfeedrations,eitheras growthpromotersorastherapeuticagents.Therefore,thesecondsectionofthis book, “Environmental Fate and Transformations of Veterinary Pharmaceuticals,” is dedicated to chapters that explore the behavior of pharmaceuticals in soil and the potential effects of antibiotics on plants after uptake. Pharmaceuticals are also introduced into the environment via wastewater treat- mentplants(WWTPs),whicharecurrentlynotdesignedandoperatedtoremove low concentrations of organic contaminants. Because increasing amounts of treated wastewaterarerecycledforindustrialanddomesticuse,itisimportanttoimprove treatment technologies for both wastewater and drinking water sources. Therefore, thethirdsectionofthisbook,“TreatmentofPharmaceuticalsinDrinkingWaterand © 2008 by Taylor & Francis Group, LLC viii Fate of Pharmaceuticals in the Environment and in Water Treatment Systems Wastewater,” includes chapters that examine various treatment processes that can be employed to reduce the concentrations of pharmaceuticals at the source. This book covers important issues regarding the analysis, occurrence, persis- tence, treatment, and transformations of pharmaceuticals in the environment. Topics range from eld studies documenting the occurrence of pharmaceuticals in sev- eral environmental compartments to laboratory studies determining the degrada- tion kinetics and formation of byproducts during treatment. This book will provide information that will help scientists, regulators, and engineers understand the factors that affect the environmental fate of pharmaceuticals in soil and water to facilitate the development of best management practices and optimize treatment systems for effective removal of these compounds in the environment. Diana S. Aga Department of Chemistry Univers ity at Buffalo Buffalo, New York © 2008 by Taylor & Francis Group, LLC ix Editor Diana Aga, Ph.D., is an associate professor of chemistry at the University at Buffalo, The State University of New York. Her current research involves the investigations on the fate, transport, and ecotoxicological effects of pharmaceuticals, endocrine- disrupting chemicals, and persistent organic pollutants in the environment. A major focusofherresearchistoidentifyunknowntransformationproductsofpharmaceu- ticals in various environmental matrices (for example, manure, plants, soil, waste- water) using a combination of novel strategies in sample preparation, bioassays, and modern mass spectrometric techniques. Dr. Aga received her B.S. in agricultural chemistry at the University of the Philippines at Los Baños (1988) and her Ph.D. in environmental and analytical chemistry at the University of Kansas (1995). She was aresearchassistantattheU.S.GeologicalSurvey,Lawrence,Kansas(1993–1996), andapostdoctoralfellowattheSwissFederalInstituteofAquaticScienceandTech- nology (EAWAG), Switzerland (1996–1998). Dr. Aga is recipient of various research awards, such as the National Science Foundation CAREER Award, the North Atlan- tic Treaty Organization Scientic and Environmental Affairs Fellowship, and the Alexander von Humboldt Research Fellowship. © 2008 by Taylor & Francis Group, LLC xi Craig D. Adams Department of Civil, Architectural, and Environmental Engineering University of Missouri at Rolla Rolla, Missouri Damià Barceló DepartmentofEnvironmental Chemistry IIQAB-CSIC Barcelona, Spain Angela Batt National Exposure Research Laboratories OfceofResearchandDevelopment U.S.EnvironmentalProtection Agency Cincinnati, Ohio James O. Berry BiologyDepartment UniversityatBuffalo Buffalo, New York Alistair B.A. Boxall CentralScienceLaboratory UniversityofYork SandHutton,York United Kingdom Nadia Carmosini DepartmentofAgronomy PurdueUniversity West Lafayette, Indiana Joel R. Coats Department of Entomology Iowa State University Ames, Iowa Michael C. Dodd SwissFederalInstituteofAquatic Science and Technology (EAWAG) Duebendorf, Switzerland Michael H. Farkas Biology Department University at Buffalo Buffalo, New York Tamara Floyd-Smith Department of Chemical Engineering Tuskegee Un iversit y Tuskegee, Alaba ma Michael J. Focazio U.S.GeologicalSurvey Reston, Virginia Edward T. Furlong U.S.GeologicalSurvey Denver, Colorado Susan T. Glassmeyer National Exposure Research Laboratory OfceofResearchandDevelopment U.S.EnvironmentalProtection Agency Cincinnati, Ohio Willie F. Harper, Jr. DepartmentofCivilEngineering AuburnUniversity Auburn, Alabama Keri L. Henderson DepartmentofEntomology Iowa State University Ames, Iowa Contributors © 2008 by Taylor & Francis Group, LLC xii Fate of Pharmaceuticals in the Environment and in Water Treatment Systems Ching-Hua Huang SchoolofCivilandEnvironmental Engineering G e orgiaInstituteofTechnology Atlanta, Georgia Sungpyo Kim DepartmentofEarthand EnvironmentalEngineering Columbia University Ne wYork Christine Klein DepartmentofChemistry Un iversityatBuffalo Buffalo, New York K.F. Knowlton DepartmentofDairyScience VirginiaPolytechnicInstituteand StateUniversity Blacksburg, Virginia Dana W. Kolpin U. S. Geological Survey Iowa City, Iowa Reinhard Länge BayerScheringPharma Nonclinical Drug Safety B e rlin, Germany Linda S. Lee De partment of Agronomy Purdue University West Lafayette, Indiana Hongxia Lei WaterQualityResearchand D e velopmentDivision Southern Nevada Water Authority La sVegas,Nevada Jonas Locke DepartmentofChemistry University at Buffalo Bu ffalo, New York N.G. Love DepartmentofCiviland EnvironmentalEngineering Virginia Polytechnic Institute and St ate University Blacksburg, Virginia Thomas B. Moorman U.S. Department of Agriculture– Agricultural Research Service (ARS) National Soil Tilth Laboratory Ames, Iowa Claudia Neubert BayerScheringPharma No nclinicalDrugSafety Berlin,Germany Seamus O’Connor DepartmentofChemistry University at Buffalo B u ffalo, New York Vanessa J. Pereira InstitutodeBiologiaExperimentale Tecnólogica Oeiras, Portugal Sandra Pérez DepartmentofEnvironmental Chemistry Consejo Superior de Investigaciones C i enticas (CSIC) Barcelona, Spain Rudolf J. Schneider DepartmentofAnalyticalChemistry: Re ferenceMaterials Federal Institute for Materials Re search and Testing Berlin, Germany Amisha D. Shah SchoolofCivilandEnvironmental Engineering Georgia Institute of Technology A tlanta, Georgia © 2008 by Taylor & Francis Group, LLC [...]... nd-0.88 nd-0.038 nd-2.6 (0.0458) nd-0. 31 nd -1 . 59 0.42 8-9 .7 1. 39 max 0.02 1- 0 .055 © 2008 by Taylor & Francis Group, LLC 3.69 only 16 .3 max 42. 4-4 3.8 50 51 127 0.22 only 4.52 max 0. 01 3-0 .036 nd-7.99 (0.0532) nd-9.9 1. 74 2-8 .13 2 0.4 6 -1 .56 0.036 ave 50 51 127 20 22 39 12 8 12 9 12 1 11 7 20 11 9 10 2 11 2 20 11 6 10 2 20 11 6 10 2 11 2 50 11 6 11 9 20 22 39 77 10 2 11 2 Fate of Pharmaceuticals in the Environment and in Water. .. 0 .1 1- 2 .17 (0. 31) 0.9 1- 2 .1 0 .12 1 med nd-27.256 (3.086) nd-22 0.00 5-0 .425 2.23 5-6 . 718 0.003 5-0 .064 0. 018 ave 0 .11 med 1. 1- 1 51 0.03 only nd-0.2 (nd) Reference 50 23 53 51 125 12 7 48 49 11 8 45 14 0 36 21 40 37 39 38 12 9 12 3 12 0 75 20 Surface -Water Concentration μg/L 0.22 max nd-0 .15 0 .14 4-2 .37 nd-0 .14 6 0. 01 max 0. 014 only 3.08 max 5.6 max nd-0.034 nd-0 .11 5 Reference 50 23 53 12 1 12 2 10 10 3 10 4 11 9 77 0. 013 ... nd-7.5 (nd) nd -1 2 .74 nd-0.0736 (0.0042) 0 .10 6 max nd-0.273 (nd) 0.023 max nd-0.0058 0.029 only 0.94 max 50 20 11 7 20 10 2 20 10 2 11 2 11 6 10 2 nd-0.08 nd-0.073 13 3 13 1 Fate of Pharmaceuticals in the Environment and in Water Treatment Systems TABLE 1. 1 (Continued) Compound enalaprilat CAS Number 7642 0-7 2-9 enrofloxacin 9 310 6-6 0-6 erythromycin 11 4-0 7-8 0.7 1- 0 .14 1 erythromycin-H2O (anyhydro-erythromycin) 11 4-0 7-8 ... (anyhydro-erythromycin) 11 4-0 7-8 0.2 ave 0.0 6-0 .19 (0.07) nd -1 . 2 0.0 9-0 .35 estrone 5 3 -1 6-7 estrone-3-sulfate ethyl citrate 54 91 0-8 9-3 Reference 0 .1 max 13 8 87 13 5 13 9 0.032 med 0.00 8-0 .052 (0. 016 ) 2.4 max 11 8 45 14 0 12 8 0 .14 5-0 .29 0.047med nd -1 . 842 (nd) 0.0 1- 0 .03 53 36 21 120 0.08 ave 0.0 6-0 .11 (0.07) nd-0.3 0.0 4-0 .12 nd-0.48 (0 .15 ) 0.05 5-0 .075 0. 013 med nd-0.054 (0.005) 4.4 max 13 8 87 13 5 13 9 20 12 4 11 8 45 14 0 0 .1 1- 0 .52... 11 6 0.0 2-0 .19 nd-0.29 (nd) nd-0 .18 0.22 max nd -1 . 1 (nd) 0.27 max nd-0.25 nd -1 . 78 (nd) nd-3.6 nd-0.066 0.555 max 0.02 5-0 .065 1. 95 max nd-0. 014 nd-0.78 (nd) 0.22 max nd-0.343 (nd) 0.0 01 med 0.003 max 0.268 max nd -1 . 3 11 7 20 11 6 10 2 20 10 2 23 20 40 12 1 10 3 11 9 10 2 11 2 20 10 2 20 36 12 2 10 3 37 nd-0.58 (nd) 0.066 max nd-0.073 20 10 2 11 2 Fate of Pharmaceuticals in the Environment and in Water Treatment Systems. .. ave 50 46 nd-0.079 nd-0. 01 nd-0.023 40 37 38 Fate of Pharmaceuticals in the Environment and in Water Treatment Systems TABLE 1. 1 (Continued) CAS Number 15 4-2 1- 2 loratadine mefenamic acid 7979 4-7 5-5 6 1- 6 8-7 metformin 65 7-2 4-9 methyl salicylate 11 9-3 6-8 metoprolol 3735 0-5 8-6 monensin n,n-diethyl-m-toluamide (DEET) 2237 3-7 8-0 13 4-6 2-3 n4-acetyl-sulfamethoxazole 213 1 2 -1 0-7 naphthalene 9 1- 2 0-3 Reference... 7 2 -1 4-0 5496 5-2 4 -1 0 .14 3-0 . 215 53 tetracycline 6 0-5 4-6 thiabendazole 14 8-7 9-8 tonalide (AHTN)* 15 0 6-0 2 -1 0.45 only nd -1 . 2 13 3 13 5 0.2 1- 1 .10 6 0.687 med 0. 9 -1 .69 49 11 8 14 0 WWTP Effluent Concentration μg/L 0.352 max 1. 3 max 0 .12 7 med nd-0 .13 2 (nd) nd -1 . 6 0.0 4-0 .35 (0.09) Reference 12 4 12 8 36 21 137 87 Surface -Water Concentration μg/L Reference 0 .12 1 only nd-0. 016 14 6 13 1 53 0 .14 6-0 .369 nd-0.042 (nd) 0 .19 ... only nd-0. 21 133 13 5 nd-0. 019 12 4 0.02 only 0.52 only 0.2 3-0 .57 (0.43) nd -1 . 25 nd-0 .14 5 nd-0.87 nd-0.674 0.58 max 0. 4 -1 2.8 50 13 3 87 13 5 49 23 13 4 14 0 13 6 0.07 only 0 .13 only 0. 21 1- 0 .86 (0.29) nd-0.37 nd-0.0 91 nd-0.82 nd-0.304 0.25 max nd-0.589 (0 .15 ) 0.3 7-6 50 13 3 87 13 5 49 23 13 4 14 0 20 22 13 3 14 6 11 6 13 1 10 2 nd-0 .19 nd-0.22 nd-0.408 nd-0.038 0. 01 max nd-0 .12 0.402 only 0.202 max nd-0.5 nd-0.009... 14 5 23 0.03 only 0 .19 5-0 .373 0.00 3-0 .16 0. 1- 0 .47 50 53 14 5 23 0.34 only 0.28 5-0 .482 0.3 2-3 . 21 (0.07) nd-22 (nd) 50 49 45 20 nd -1 . 1 11 6 nd-0.68 nd-0.34 (nd) 11 6 20 nd-0 .13 oxytetracycline 50 49 45 Surface -Water Concentration μg/L nd-0 .10 9 0.03 31 med 13 3 0.78 max 50 0.2 max nd-0 .18 nd -1 . 2 nd -1 2 (nd) 0.88 max nd-0.085 50 11 7 11 6 20 10 2 12 1 0. 01 max 0.03 7-0 .10 7 nd-0.032 50 53 14 5 21 (Continued) © 2008 by... nd -1 . 6 4.3 max 20 11 6 13 3 13 1 10 2 20 11 6 10 2 Environmental Presence and Persistence of Pharmaceuticals Compound camphor WWTP In uent Concentration μg/L (Continued) 11 © 2008 by Taylor & Francis Group, LLC 12 WWTP In uent Concentration μg/L Compound cimetidine CAS Number 514 8 1- 6 1- 9 ciprofloxacin 8572 1- 3 3 -1 0.0 9-0 .3 0.228 max nd-0. 21 3. 6 -1 01 clarithromycin 811 0 3 -1 1- 9 0.3 3-0 .6 (0.38) 0.647 clindamycin 18 32 3-4 4-9 . 8 0-0 5-7 0.7 2-2 .376 0.2 1- 2 .4 (1. 28) 49 45 0.02 6 -1 .53 0.0 2-0 .45 (0 .18 ) nd-0. 31 (0 .12 ) 49 45 20 nd-0 .11 4 0.0 1- 0 .02 nd-0.3 (nd) nd-0 .14 7 0.7 max nd-0.23 12 1 11 7 20 11 9 10 2 11 2 bromacil 31 4-4 0-9 nd-0.69. nd a -0 . 91 (0 .11 ) 20 nd-0.28 (nd) 0.02 7-0 .098 0.095 max b 20 11 6 10 2 1, 7-dimethylxanthine 61 1-5 9-6 nd-8.55 (nd) 20 nd -1 . 76 (nd) 0.294 max 20 10 2 17 -alpha-ethynyl estradiol 5 7-6 3-6 0. 1- 0 .13 11 7 17 -beta-estradoil. (nd) nd-0 .18 0.22 max 11 7 20 11 6 10 2 5-methyl-1h-benzotriazole 13 6-8 5-6 nd -1 . 7 (0.82) 20 nd -1 . 1 (nd) 0.27 max 20 10 2 acetaminophen 10 3-9 0-2 0 .1 3-2 6.09 5.52 9-6 9.57 23 53 nd-5.99 nd -1 . 06 (0.006) nd-9 0. 5-2 9 23 20 40 12 0 nd-0.25 nd -1 . 78