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Phytoforensics on Energetics: Novel Plant Tissue Measure Approach and Modeling

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Phytoforensics on Energetics: Novel Plant Tissue Measure Approach and Modeling Scholars' Mine Doctoral Dissertations Student Theses and Dissertations Spring 2013 Phytoforensics on energetics: novel plant tissue measure approach and modeling Yuan Yuan Follow this and additional works at: https://scholarsmine.mst.edu/doctoral_dissertations Part of the Civil and Environmental Engineering Commons Department: Civil, Architectural and Environmental Engineering Recommended Citation Yuan, Yuan, "Phytoforensics on energetics: novel plant tissue measure approach and modeling" (2013). Doctoral Dissertations. 2236. https://scholarsmine.mst.edu/doctoral_dissertations/2236 This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. PHYTOFORENSICS ON ENERGETICS: NOVEL PLANT TISSUE MEASURE APPROACH AND MODELING by YUAN YUAN A DISSERTATION Presented to the Faculty of the Graduate School of the MISSOURI UNIVERSITY OF SCIENCE AND TECHNOLOGY In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY in CIVIL ENGINEERING 2013 Approved by: Joel Burken, Advisor Honglan Shi Glenn Morrison Mark Fitch Yinfa Ma 2013 YUAN YUAN All Rights Reserved iii ABSTRACT Explosives and energetics are common soil and groundwater pollutions. This research was to develop novel phytoforensics approaches on energetics. Four different plants species, including woody perennial trees and monocot grasses, were planted both in soil and sand reactors with continuous exposure to a mixture of explosives in the greenhouse. Time dependent assessments were carried out to determine kinetic mechanisms of uptake, transport and accumulation. Plant concentrations were analyzed by both traditional solvent extraction and novel sap analysis methods. A dynamic soil- plant system model was developed to quantify the relationship between tissue concentration and soil pore water concentration for non-volatile organic chemicals with root pathway only. The model included processes of diffusion exchange between root and soil, mass flow in xylem, metabolism and chemical equilibrium in soil and plant interior. The novel plant analysis method with sap extracted by freeze-centrifuge treatments was validated by solvent extract method on the range of plant species and tissues. The novel approach is rapid, cost effective and labor saving and does not require any soil or water sampling, thereby can access vast field samples not practical previously. The Stella® soil-plant system model was effective in estimating the concentrations in soil pore water, plant sap and tissue from dosing concentration input in the experimental settings of this work. The model can be applied for non-volatile compounds and different conditions with only minor adaptions and might be the base of improvement of soil-plant system models for phytoforensics. The phytoforensic approach was validated on RDX and HMX by both experimental results and simulated results as strong correlation were achieved between plant concentration and exposure concentration. iv ACKNOWLEDGMENTS First and foremost, I would like to acknowledge my advisor, Dr. Joel Burken, for his invaluable advice and help in his busy schedule, and his patience and kindness to put up with my weak English communication. Without him, this work could have never been done. I would like to thank all my committee members, Dr. Honglan Shi, Dr. Yinfa Ma, Dr. Glenn Morrison and Dr. Mark Fitch. Special thanks are given to Dr. Shi and Dr. Ma. They helped a lot in this work. The HPLC-MS/MS analysis method and sap sampling method were developed under their direct guidance. They were also concerned about the progress of the work, reviewed all experimental data, and provided numerous key advices. I would like to thank Dr. Adcharee „Fa‟ Karnjanapiboonwong, Ruipu Mu, Xiaojing Wang, the group members in this work. Special thanks are given to Ruipu Mu. He finished most of samples analysis by LC-MS/MS. Fa developed the solvent extraction method used in this study and reviewed my early manuscript. I would like to thank the Leonard Wood Institute (LWI) for funding this research. Dr. Jason Baird kindly provided explosive compounds used in this work. I am grateful to my colleagues at Environmental Engineering Department and the Environmental Research Center for their assistance. Matt Limmer gave many helpful advices and greenhouse expertise; Amanda Holmes helped to dose plants when I was traveling; Ryan Stringer and Guoqiang Liu helped to take tree cores. v TABLE OF CONTENTS Page ABSTRACT ....................................................................................................................... iii ACKNOWLEDGMENTS ................................................................................................. iv LIST OF ILLUSTRATIONS ............................................................................................. ix LIST OF TABLES ............................................................................................................. xi NOMENCLATURE ......................................................................................................... xii SECTION 1. INTRODUCTION .............................................................................................. 1 1.1. BACKGROUNDING ................................................................................. 1 1.2. TECHNICAL GOAL AND OBJECTIVES ................................................ 5 1.3. SIGNIFICANCE ......................................................................................... 8 1.4. COLLABORATOR WORKS ..................................................................... 8 2. REVIEW OF LITERATURE ........................................................................... 10 2.1. PROPERTIES AND ENVIRONMENTAL FATE ................................... 10 2.2. INTERACTION BETWEEN SOIL AND EXPLOSIVES ....................... 11 2.2.1. TRANSFORMATION IN SOIL .................................................... 11 2.2.2. SORPTION IN SOIL ...................................................................... 15 2.3. INTERACTION BETWEEN PLANTS AND EXPLOSIVES ................. 17 2.3.1. TOXICOLOGICAL PROFILES .................................................... 17 2.3.2. UPTAKE AND DISTRIBUTION .................................................. 20 2.3.3. METABOLISM PATHWAYS ....................................................... 25 2.4. PLANTS MODELING ............................................................................. 28 vi 3. MATERIALS AND METHODS ...................................................................... 39 3.1. CHEMICALS ............................................................................................ 39 3.2. PLANTS, SOIL AND SAND ................................................................... 39 3.3. BATCH SORPTION TEST ...................................................................... 40 3.4. SHORT-TERM HYDROPONIC PLANTING EXPERIMENT ............... 41 3.5. SMALL SCALE TREE AND GRASS EXPERIMENTS ........................ 42 3.6. TIME-SERIES GRASS EXPERIMENTS ................................................ 45 3.7. LARGE SCALE TREE AND LONG TERM EXPERIMENTS .............. 47 3.8. PLANT TISSUE AND SAP ANALYSIS................................................. 48 3.8.1. SOLVENT EXTRACTION METHOD .......................................... 48 3.8.2. CENTRIFUGE EXTRACTION METHOD ................................... 49 3.8.3. HPLC-MS/MS ANALYSIS............................................................ 50 3.9. DATA TREATMENT AND ANALYSIS ................................................ 52 3.10. FULL SCALE FIELD ASSESSMENT .................................................. 53 4. PLANT MODELING ....................................................................................... 57 4.1. CONCEPTUAL MODEL ......................................................................... 57 4.2. MASS BALANCE EQUATIONS ............................................................ 59 4.3. STELLA MODEL ..................................................................................... 63 5. RESULTS AND DISCUSSION ....................................................................... 67 5.1. BATCH SORPTION TEST ...................................................................... 67 5.1.1. SORPTION ON ROOTING MEDIA ............................................. 67 5.1.2. SORPTION ON PLANT TISSUES................................................ 70 5.2. DEVELOP THE NOVEL PLANT ANALYSIS METHODS .................. 72 vii 5.2.1. CENTRIFUGE EXTRACTION METHOD OPTIMIZATION ..... 72 5.2.2. CENTRIFUGE EXTRACTION EFFICIENCY ............................. 72 5.2.3. COMPARISON OF EXTRACTED SAP CONCENTRATION TO TISSUE CONCENTRATION ................................................. 73 5.3. THE ROLE OF BACTERIA DEGRADATION AND SOIL SORPTION ............................................................................................... 75 5.4. TIME DEPENDENT TISSUE CONCENTRATION ............................... 78 5.4.1. TIME DEPENDENT TISSUE CONCENTRATION ON GRASSES ...................................................................................... 78 5.4.2. TIME DEPENDENT TISSUE CONCENTRATION ON TREES . 86 5.5. SPATIAL DEPENDENT TISSUE CONCENTRATION ........................ 88 5.6. EXPOSURE CONCENTRATION DEPENDENT TISSUE CONCENTRATION................................................................................
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