JDGillis Thesis

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i Monitoring organic contaminant concentrations and carbon mineralization in field soils receiving alkaline-stabilized biosolids by Joseph Daniel Gillis Submitted in partial fulfillment of the requirements for the degree of Master of Science at Dalhousie University Halifax, Nova Scotia in cooperation with Nova Scotia Agricultural College Truro, Nova Scotia April 2011 J.D. Gillis, 2011 ii DALHOUSIE UNIVERSITY NOVA SCOTIA AGRICULTURAL COLLEGE The undersigned hereby certify that they have read and recommend to the Faculty of Graduate Studies for acceptance a thesis entitled Monitoring organic contaminant concentrations and carbon mineralization in field soils receiving alkaline-stabilized biosolids by Joseph Daniel Gillis in partial fulfillment of the requirements for the degree of Master of Science Dated: Supervisor: Readers: iii DALHOUSIE UNIVERSITY AND NOVA SCOTIA AGRICULTURAL COLLEGE DATE: AUTHOR: Joseph Daniel Gillis TITLE: Monitoring organic contaminant concentrations and carbon mineralization in field soils receiving alkaline-stabilized biosolids DEPARTMENT OR SCHOOL: DEGREE: Master of Science CONVOVATION: YEAR: Permission is herewith granted to Dalhousie University to circulate and to have copied for non-commercial purposes, at its discretion, the above title upon the request of individuals or institutions. Signature of Author The author reserves other publication rights, and neither the thesis nor extensive extracts from it may be printed or otherwise reproduced without the authors written permission. The author attests that permission has been obtained for the use of any copyrighted material appearing in the thesis (other than the brief excerpts requiring only proper acknowledgement in scholarly writing), and that all such use is clearly acknowledged. iv DEDICATION To my parents, for encouraging me to always do the best that I could, and to Richard and Clara, for allowing me to take the road less travelled. v TABLE OF CONTENTS LIST OF TABLES viii LIST OF FIGURES ix ABSTRACT x LIST OF ABBREVIATIONS AND SYMBOLS USED xi ACKNOWLEDGEMENTS xii CHAPTER 1: REVIEWING THE IMPACTS FROM LAND APPLICATION OF SEWAGE BIOSOLIDS ON ORGANIC CONTAMINANT CONCENTRATIONS 1 1. Introduction 1 1.1. Thesis Objectives 2 2. Biosolids in Canada 3 2.1. What is a Biosolid? 3 2.2. Alkaline-Stabilized Biosolids 4 2.3. Sources and Types of Organic Contaminants in Wastewater Treatment 5 2.3.1. Persistent Organic, Toxic, and Priority Pollutants 6 2.3.1.1. Phenanthrene and Benzo[a]pyrene 7 2.3.1.2. p-Cresol 8 2.3.1.3. Indole 9 2.3.2. Brominated Flame Retardants 9 2.3.3. Pharmaceuticals and Personal Care Products 10 2.3.3.1. 4-t-Octylphenol (4-t-OP) 11 2.3.3.2. Triclosan 12 2.3.3.3. Carbamazepine 13 3. Challenges in Analyzing Environmental Samples for Organic Contaminants 14 3.1. Soil Sampling and Handling for Trace Organic Compounds 15 3.1.1. Soil Sampling 15 3.1.2. Problems Posed by the Soil Matrix 17 3.2. Extraction 18 3.2.1. Sample Preparation and Solvent Choice 18 3.2.2. Extraction Techniques 19 3.3. Sample Cleanup 21 3.3.1. Liquid-Liquid Extraction 22 3.3.2. Column Chromatography and SPE 23 3.4. Analysis by Gas Chromatography with Mass Spectrometry (GC-MS) 24 4. Conclusions 25 vi CHAPTER 2: DECOMPOSITION OF N-VIRO SOIL IN AN AMENDED FIELD SOIL 27 1. Introduction 27 2. Materials and Methods 29 2.1. Sampling and Handling 29 2.2. Experimental Design 31 2.3. Soil and Biosolid Properties 31 2.4. Statistical Methods 32 2.5. Development of FLOG Model 32 3. Results and Discussion 35 3.1. Carbon Mineralization and Model Fits 35 3.2. Theoretical Considerations 38 4. Conclusions 42 CHAPTER 3: EVALUATION OF AN ULTRASONIC EXTRACTION METHOD FOR DETERMINATION OF DIFFERENT CLASSES OF PRIORITY ORGANIC CONTAMINANTS IN AN AGRICULTURAL FIELD SOIL 44 1. Introduction 44 2. Materials and Methods 46 2.1. Chemicals and Materials 46 2.2. Soil Sampling and Processing 47 2.3. Ultrasonic Extraction and Cleanup 47 3. Results and Discussion 48 3.1. Linear Range of Analyte Concentration 48 3.2. Precision and Recovery 48 3.3. Ruggedness Testing 57 3.3.1. Comparison of Phosphate Buffer Wash vs. Mixed With Sample 57 3.3.2. Investigating Effect of Analyte Concentration and Florisil Cartridge on Recovery 59 3.3.3. Effect of SPE Cartridge Brand and Spiking Concentration on Percent Recovery 60 3.3.4. Biosolids-Amended Soil Samples From Incubation 61 4. Conclusions 64 CHAPTER 4: TRICLOSAN CONCENTRATION OVER TIME IN AN AGRICULTURAL SOIL AMENDED WITH A HIGH RATE OF AN ALKALINE-STABILIZED BIOSOLID 65 1. Introduction 65 2. Materials and Methods 67 2.1. Chemicals and Materials 67 2.2. Soil Sampling and Processing 67 2.3. Method Performance 68 3. Results and Discussion 69 3.1. Triclosan Concentration in Soil 69 4. Conclusions 74 vii CHAPTER 5: OVERALL CONCLUSIONS 76 1. Overall Conclusions 76 APPENDIX I: STANDARD OPERATING PROCEDURES FOR ULTRASONIC EXTRACTION OF ORGANIC CONTAMINANTS FROM SOIL WITH SOLID PHASE EXTRACTION CLEANUP FOR ANALYSIS BY GAS CHROMATOGRAPHY-MASS SPECTROSCOPY 78 1. Scope of Method 78 2. Matrix Characterization 78 3. Standard Operating Procedures 78 3.1. Preparation of Solvent Mixtures 78 3.1.1. 80:20 Dichloromethane:Diethyl Ether 78 3.1.2. 80:20 Isopropyl Alcohol:Water 79 3.1.3. 0.1 M Phosphate Buffer 79 3.2. Preparation of Stock Solutions 79 3.2.1. Description 79 3.2.2. 4000 g mL-1 Internal Standards 79 3.2.3. 125 g mL-1 Stock Solution in 80:20 DCM:DEE 79 3.2.4. 5 g mL-1 Spiking Standards in Scetone 79 3.3. Preparation of Standards 80 3.4. Internal Standard Calculations 80 3.5. Soil Preparation 81 3.6. Ultrasonic-Assisted Extraction, 3 x 10 min 81 3.7. Centrifugation 82 3.8. Solid-Phase Extraction Cleanup 82 3.9. Concentration 83 3.10. Sample Storage and Handling 83 3.11. Analysis by GC-MS 83 REFERENCES 85 viii LIST OF TABLES Table 1 Selected models describing cumulative carbon dioxide evolution from soil over time. 29 Table 2 Chemical properties of agricultural field soil and alkaline-stabilized biosolids (NVS). Values are expressed on a dry weight basis. 29 Table 3 Comparison of statistical measures of model adequacy of selected functions used to model cumulative CO2-C evolution from soil. 33 Table 4 Comparison of parameter estimates for FO, FLIN, DFO, and FLOG models. 37 Table 5 Retention time (minutes) and quantifying and qualifying ionsa (m/z), spiking concentration, limits of detection and quantification (LOD and LOQ, ng g-1 soil) calculated as Mean + 3 and 10 Standard Error (n=9), and percent recovery for each compound. 56 Table 6 Triclosan concentration (ng g-1) in the top 15 cm of field plots receiving annual biosolid applications. 70 ix LIST OF FIGURES Figure 1. Cumulative carbon mineralization from soil at increasing biosolid amendment rates (mg biosolids g-1 soil d.w.). Curves are modeled using the FO model (A), FLIN model (B), DFO model (C), and FLOG model (D). 34 Figure 2. Simulated CO2-C evolution (A) and mineralization rate curves (B) using the FLOG model (Table 1). 40 Figure 3. Calibration curve for p-cresol using combined data from method evaluation studies containing internal standard. 49 Figure 4. Calibration curve for indole using combined data from method evaluation studies containing internal standard. 50 Figure 5. Calibration curve for 4-t-octylphenol using combined data from method evaluation studies containing internal standard. 51 Figure 6. Calibration curve for phenanthrene using combined data from method evaluation studies containing internal standard. 52 Figure 7. Calibration curve for triclosan using combined data from method evaluation studies containing internal standard. 53 Figure 8. Calibration curve for carbamazepine using combined data from method evaluation studies containing internal standard. 54 Figure 9. Calibration curve for benzo[a]pyrene using combined data from method evaluation studies containing internal standard. 55 Figure 10. Comparison of buffer treatment (wash vs. mix) during extraction of sand spiked at 5 g g-1. 58 Figure 11. Effect of concentration on analyte recovery from spiked extraction solvent with and without Florisil cartridge cleanup. 60 Figure 12. Comparison of Phenomenex vs. Waters SPE cartridges at two soil spiking concentrations (0.2 and 2.0 g g-1 soil). 61 Figure 13. Percent recovery from spiked soils during extraction of incubation samples. 63 Figure 14. Triclosan concentration over time from incubation soil amended with 12.48 mg g-1 d.w. of NVS. 63 Figure 15. Triclosan concentration over time in amended incubation soils. 69 x ABSTRACT The application of municipal sewage biosolids to agricultural land is a common practice worldwide. Increasing attention is being directed at the presence of organic contaminants bound to the organic phase during wastewater treatment, which end up in the biosolids. The goal of this study was to investigate the decomposition of an alkaline treated biosolid being used as an agricultural soil amendment containing unknown organic contaminants. A two year field trial and a 120 day laboratory soil incubation using increasing rates (0, 7, 14, 28, and 42 Mg ha-1) of an alkaline-stabilized biosolid (N-Viro Soil) were set up to monitor biosolid decomposition and concentrations of selected contaminants over time. The seven contaminants selected for monitoring (p-cresol, indole, 4-t-octylphenol, phenanthrene, triclosan, carbamazepine, and benzo[a]pyrene) represent a wide range of physico-chemical properties and fall unde