Sorption, Degradation, and Transport of Sulfamethazine in Soils and Manure-Amended Soils Warisara Lertpaitoonpan Iowa State University
Total Page：16
File Type：pdf, Size：1020Kb
CORE Metadata, citation and similar papers at core.ac.uk Provided by Digital Repository @ Iowa State University Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2008 Sorption, degradation, and transport of sulfamethazine in soils and manure-amended soils Warisara Lertpaitoonpan Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Civil and Environmental Engineering Commons Recommended Citation Lertpaitoonpan, Warisara, "Sorption, degradation, and transport of sulfamethazine in soils and manure-amended soils" (2008). Graduate Theses and Dissertations. 11180. https://lib.dr.iastate.edu/etd/11180 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Sorption, degradation, and transport of sulfamethazine in soils and manure- amended soils by Warisara Lertpaitoonpan A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Civil Engineering (Environmental Engineering) Program of Study Committee: Say Kee Ong, Co-major Professor Thomas B. Moorman, Co-major Professor Thomas E. Loynachan Timothy G. Ellis Roy Gu Iowa State University Ames, Iowa 2008 Copyright © Warisara Lertpaitoonpan, 2008. All rights reserved. ii TABLE OF CONTENTS LIST OF TABLES iv LIST OF FIGURES v ACKNOWLEDGEMENTS viii ABSTRACT x CHAPTER 1. INTRODUCTION ………………………………………………… 1 1.1 General introduction…………………………………………………… 1 1.2 Dissertation organization………………………………………………. 3 1.3 References……………………………………………………………... 4 CHAPTER 2. LITERATURE REVIEW ……………………………………......... 7 2.1 Antibiotics usage………………………………………………………. 7 2.2 Environmental and human risks……………………………………….. 8 2.3 Characteristics of sulfamethazine……………………………………… 9 2.4 Environmental concentrations…………………………………………. 14 2.5 Fate of sulfonamides in the environment……………………………… 18 2.5.1 Sorption……………………………………………………….. 18 2.5.2 Impact of soil pH on sorption of sulfonamides……………….. 22 2.5.3 Degradation…………………………………………………… 22 2.6 Transport of sulfonamides……………………………………………... 25 2.7 Summary……………………………………………………………….. 26 2.8 References……………………………………………………………... 27 CHAPTER 3. EFFECT OF ORGANIC CARBON AND PH ON SOIL SORPTION OF SULFAMETHAZINE………………............................................ 39 3.1 Abstract……………………………………………………………….... 39 3.2 Introduction……………………………………………………………. 40 3.3 Materials and methods…………………………………………………. 41 3.3.1 Soil sampling and analysis……………………………………. 41 3.3.2 Chemicals……………………………………………………... 42 3.3.3 HPLC analysis………………………………………………… 43 3.3.4 Batch sorption experiments…………………………………… 43 3.4 Results and discussion…………………………………………………. 45 3.4.1 Sorption isotherms…………………………………………….. 45 3.4.2 Effect of pH…………………………………………………… 46 3.4.3 Model development…………………………………………… 48 3.5 Conclusion…………………………………………………………….. 51 3.6 References…………………………………………………………….. 52 iii CHAPTER 4. DEGRADATION OF SULFAMETHAZINE IN SOIL AND MANURE-AMENDED SOIL ……………………………………………... 67 4.1 Abstract……………………………………………………………….... 67 4.2 Introduction……………………………………………………………. 68 4.3 Materials and methods…………………………………………………. 70 4.3.1 Soil sampling and swine manure…………………………….... 70 4.3.2 Chemicals……………………………………………………... 71 4.3.4 Sulfamethazine effects on microbial respiration……………… 71 4.3.5 Aerobic degradation of SMZ………………………………….. 73 4.3.6 Anaerobic degradation of SMZ……………………………….. 74 4.3.7 Extraction of SMZ…………………………………………….. 75 4.3.8 HPLC analysis………………………………………………… 75 4.3.9 Fate of 14 C-SMZ………………………………………………. 76 4.4 Degradation kinetics…………………………………………………… 77 4.5 Results and discussion…………………………………………………. 78 4.5.1 SMZ effects on microbial respiration…………………………. 78 4.5.2 Aerobic and anaerobic degradation of SMZ…………………... 81 4.5.3 Fate of 14 C-SMZ………………………………………………. 84 4.6 Conclusion……………………………………………………………... 86 4.7 References……………………………………………………………... 87 CHAPTER 5. LEACHING OF SULFAMETHAZINE IN SOIL WITH AND WITHOUT MANURE: EFFECT OF DURATION BETWEEN APPLICATION AND RAIN ……………………………………………………………………….. 104 5.1 Abstract………………………………………………………………… 104 5.2 Introduction……………………………………………………………. 105 5.3 Materials and methods…………………………………………………. 107 5.3.1 Soil and swine manure sampling and analysis………………... 107 5.3.2 Chemicals……………………………………………………... 108 5.3.3 Soil column preparation………………………………………. 108 5.3.4 Leaching study………………………………………………… 109 5.3.5 Samples clean up using SPE…………………………………... 111 5.3.6 Soil extraction…………………………………………………. 111 5.3.7 HPLC analysis………………………………………………… 112 5.4 Results and discussion…………………………………………………. 113 5.5.1 Effect of time duration and manure on SMZ leaching………... 113 5.5.2 Depth distribution of SMZ……………………………………. 115 5.5 Conclusion……………………………………………………………... 117 5.6 References……………………………………………………………... 118 CHAPTER 6. CONCLUSION …………………………………………………... 129 iv LIST OF TABLES CHAPTER 2 Table 1 List of sulfonamides (Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals, 2001)……………………….. 11 Table 2 Concentrations of sulfonamides in manure, soils, and water ……. 16 Table 3 Sorption coefficients of sulfonamides at various conditions ….… 20 CHAPTER 3 Table 1 Physical-chemical properties of soils…………………………….. 56 Table 2 Estimated sorption coefficients, K d and K oc , with 95 % confidence interval, and Freundlich sorption coefficients (K f), nonlinearity constant (n) for five soils for pH from 5.5 to 9……... 57 + 0 - Table 3 Kd , K d , and Kd for five soils…………………………………… 58 Table 4 Comparison of mean estimated K oc for four soils (excluding Clarion-1) at each pH and the K oc predicted by Eq. 7 using one- sample t test………………………………………………………. 59 Table 5 Comparison of K d reported by other researchers and predicted K d using Eqs. 2 – 5 and Eq. 6………………………………………... 60 CHAPTER 4 Table 1 Degradation rate constants and half-lives of aerobic degradation, and anaerobic degradation of SMZ in soils alone and manure- amended soils (with 95 % confidence interval)………………….. 92 Table 2 Fraction of total 14 C, and 14 C-SMZ in extracts after 28 and 77 days incubation under aerobic and anaerobic conditions, respectively (average with 95 % confidence interval)…………… 93 CHAPTER 5 Table 5.1 Physical-chemical characteristics of soil for each depth increment 124 v LIST OF FIGURES CHAPTER 2 Figure 1 Chemical structures of PABA and sulfonamide group…………... 9 Figure 2 Chemical structure of sulfamethazine and its protonated and deprotonated form………………………………………………... 13 CHAPTER 3 Figure 1 Chemical structure of sulfamethazine and its anionic and cationic forms……………………………………………………………... 61 Figure 2 Sorption isotherms of sulfamethazine for five soils at pH 5.5, 6, 7, 8, and 9. Solid lines show the linear isotherms obtained by least squares regression…………………………………………... 62 Figure 3 Sorption (K d) of sulfamethazine to five soils (Clarion-1, Clarion- 2, Clarion-3, Nicollet, and Harps) as a function of (a) pH, and (b) percent of anionic sulfamethazine in solution……………………. 63 Figure 4 Relationship of sulfamethazine sorption and soil organic carbon.. 64 Figure 5 Relationship of K oc (except for Clarion-1) and soil pH………….. 65 Figure 6 Plot of experimental K d and predicted K d predicted using Eqs. 2 – 5 and Eq. 6……………………………………………………... 66 CHAPTER 4 Figure 1 Structure of sulfamethazine……………………………………… 94 Figure 2 Net cumulative amounts of CO 2 evolved at initial SMZ concentrations of 0.5, 5, 10, 50, 100, and 150 mg kg-1 soil in soils alone and manure-amended soils under aerobic conditions over a 40-day incubation……………………………………………...….. 95 Figure 3 Net cumulative amounts of CO 2 evolved at initial SMZ concentrations of 0.5, 5, 10, 50, 100, and 150 mg kg-1 soil, in soils alone and manure-amended soil under anaerobic conditions over a 80-day incubation…………………………………………………. 96 vi Figure 4 Maximum net cumulative CO 2 evolved from soils alone and manure-amended soils under aerobic (40-day incubation) and anaerobic (80-day incubation) for various SMZ initial concentrations…………………………………………………… 97 Figure 5 Percent of extractable sulfamethazine (SMZ) remaining in (a) soils alone and (b) manure-amended soils, under aerobic conditions, for various initial SMZ concentrations (points are experimental, and solid lines are fitted results of availability adjusted first-order kinetic model)……………………………….. 98 Figure 6 Percent of extractable sulfamethazine (SMZ) remaining in (a) soils alone (b) manure-amended soils, under anaerobic conditions for various initial concentrations (points are experimental, and solid lines are fitting results of availability adjusted first-order kinetic model)……………………………….. 99 Figure 7 Adjusted rate constant (k´´) and initial SMZ concentration in aerobic (28-day incubation) and anaerobic degradation (63-day incubation) experiments for various initial SMZ concentrations…………………. 100 Figure 8 Half-lives (t 1/2 ) and initial SMZ concentration in aerobic (28-day incubation) and anaerobic degradation (63-day incubation) experiments for various initial SMZ concentrations………………….. 101 14 14 14 14 Figure 9 C mass balances for CO 2 evolved, Cextracted, and C bound residues in (a) soils alone and (b) manure-amended soils over 28-day period of aerobic degradation………………………………………. 102 14 14 14 14 Figure 10 C Mass balances for CO 2 evolved, C extracted, and C bound residues in (a)