Sorption, degradation, and transport of sulfamethazine in soils and manure-amended soils

144 Pages·2017·0.62 MB·English

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
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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
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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 14C-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 14C-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 and K , with 95 %
d oc
confidence interval, and Freundlich sorption coefficients (K),
f
nonlinearity constant (n) for five soils for pH from 5.5 to 9……... 57

Table 3 K +, K 0, and Kd- for five soils…………………………………… 58
d d

Table 4 Comparison of mean estimated K for four soils (excluding
oc
Clarion-1) at each pH and the K predicted by Eq. 7 using one-
oc
sample t test………………………………………………………. 59

Table 5 Comparison of K reported by other researchers and predicted K
d 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 14C, and 14C-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 ) of sulfamethazine to five soils (Clarion-1, Clarion-
d
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 (except for Clarion-1) and soil pH………….. 65
oc

Figure 6 Plot of experimental K and predicted K predicted using Eqs. 2
d d
– 5 and Eq. 6……………………………………………………... 66

CHAPTER 4

Figure 1 Structure of sulfamethazine……………………………………… 94

Figure 2 Net cumulative amounts of CO evolved at initial SMZ
2
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 evolved at initial SMZ
2
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 evolved from soils alone and
2
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 ) and initial SMZ concentration in aerobic (28-day
1/2
incubation) and anaerobic degradation (63-day incubation)
experiments for various initial SMZ concentrations………………….. 101

Figure 9 14C mass balances for 14CO evolved, 14Cextracted, and 14C bound
2
residues in (a) soils alone and (b) manure-amended soils over 28-day
period of aerobic degradation………………………………………. 102

Figure 10 14C Mass balances for 14CO evolved, 14C extracted, and 14 C bound
2
residues in (a) soils alone (b) manure-amended soils over 77-day
period of anaerobic degradation…………………………………….. 103

CHAPTER 5

Figure 1 Chemical structure of sulfamethazine and its anionic and cationic
forms……………………………………………………………... 125

Figure 2 Concentration (± 95 % confidence interval) of SMZ in leachate,
of soil with and without manure applied, from first and second
rain. SMZ was applied 1 day, 4 days, and 7 days before first rain.
The second rain occurred 3 days after the first rain……………… 126
vii
Figure 3 Depth concentration (± 95 % confidence interval) distributions of
SMZ in soil, with and without manure, after two rain events……. 127

Figure 4 Mass balances (± 95 % confidence interval) for SMZ after two
rain events showing SMZ leached and in soils for (a) soils treated
with SMZ or (b) SMZ and manure-amended soils (100 % SMZ
initially applied)………………………………………………….. 128
viii
ACKNOWLEDGEMENTS

There are many people who have assisted me in the completion of this dissertation. I
could never have reached the heights or explored the depths without the help, support,
guidance and efforts of these individuals. I owe my deep gratitude to all these individuals
who have made this dissertation possible, and my graduate experience unforgettable. I would
like to express my extreme appreciation to my advisor, Dr. Say Kee Ong, for his invaluable
support, patience, constructive criticisms at different stages of my research, and
encouragement throughout my graduate studies. His intimate technical and editorial advice
was essential to the completion of this dissertation and has taught me innumerable lessons
and insights on the workings of academic research in general. I would also like to extend
profound gratitude to Dr. Thomas Moorman, my co-advisor, for his enthusiastic guidance and
for always being extremely supportive and patient with all my technical and administrative
challenges that I encountered during my studies. I wish to thank Elizabeth Douglass who
kindly taught me all laboratory techniques. She was always patient with me when I worked
in the laboratory and when the lab workspace became messy. I am grateful to my committee
members, Dr. Timothy Ellis, Dr. Roy Gu, and Dr. Thomas Loynachan, who supported me
through this exciting and challenging journey.
I would like to thank several individuals at USDA-ARS where I conducted my
experiments. First is Dr. Timothy Parkin at National Soil Tilth Laboratory who allowed me
to work in his laboratory for carbon and methane analysis using GC. Second is Amy Morrow
for her analysis of sulfamethazine metabolites using LC-MS and MRM MS/MS. Last is
ix
Jennifer Cook at Swine Odor and Manure Management Research who worked on swine
manure carbon and nitrogen analysis for me.
I am also thankful to Kathy Petersen and all staff at Civil, Construction, and
Environmental Engineering Department for their administrative supports.
I extend many thanks to my colleagues and friends, especially Chu-Lin Cheng,
Naroon Waramit, Chorthip Peeraphatdit, and Pylin Sarobol, who have helped me stay
through these difficult years. Their support and care helped me overcome setbacks and stay
focused on my graduate study. I greatly value their friendship.
Importantly, none of this would have been possible without the love and patience of
my parents. I would like to express my heart-felt gratitude to my family.
Last but not least, I am very much thankful to Sripatum University and the Royal Thai
Government for sponsoring my academic study. Without their funding, it would have been
impossible for me to have a valuable experience at Iowa State University.