FINAL REPORT Developing Quantum Chemical and Polyparameter Models for Predicting Environmentally Significant Parameters for New Munition Compounds SERDP Project ER-1734 MAY 2017 Dominic M. Di Toro Herbert E. Allen Stanley I. Sandler Dave Ta Fu Kuo Tifany L. Torralba–Sanchez Yuzhen Liang University of Delaware Newark, DE Ronald T. Checkai Roman G. Kuperman Michael Simini U.S. Army Edgewood Chemical Biological Center Geoffrey I. Sunahara Jalal Hawari Sabine G. Dodard National Research Council Canada, Biotechnology Research Institute Distribution Statement A Page Intentionally Left Blank This report was prepared under contract to the Department of Defense Strategic Environmental Research and Development Program (SERDP). The publication of this report does not indicate endorsement by the Department of Defense, nor should the contents be construed as reflecting the official policy or position of the Department of Defense. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the Department of Defense. Page Intentionally Left Blank Page Intentionally Left Blank TABLE OF CONTENTS LIST OF TABLES ...................................................................................................... viii LIST OF FIGURES ..................................................................................................... xiv LIST OF ACRONYMS ............................................................................................. xxix KEYWORDS ........................................................................................................... xxxii ACKNOWLEDGEMENTS .................................................................................... xxxiii ABSTRACT ............................................................................................................. xxxiv 1 OBJECTIVES AND BACKGROUND .............................................................. 1 1.1 Overall Objective ....................................................................................... 1 1.2 Abraham Polyparameter Model ................................................................. 2 1.2.1 Estimating Abraham Solute Parameters ........................................ 4 1.2.2 ABSOLV Estimates of Abraham Solute Parameters for Munitions Compounds .................................................................................... 5 1.2.3 Quantum Chemical Estimates of Abraham Solute Parameters for Munitions Compounds ................................................................... 6 1.3 Bioconcentration Model for Plants ............................................................ 9 1.3.1 Plant-Water Partitioning ................................................................ 9 1.3.2 Plant-Cuticle Partitioning Model ................................................. 10 1.3.3 Plant Concentration Model .......................................................... 12 1.4 Bioconcentration Model for Oligochaetes ............................................... 13 1.4.1 Lipid-Water and Protein-Water Partitioning ............................... 14 1.4.2 Lipid–Water and Protein–Water pp–LFERs and Prediction of Oligochaete BCFs ........................................................................ 14 1.5 Bioconcentration Model for Fish ............................................................. 17 1.6 Model Performance and Applicability to Munitions Compounds ........... 20 REFERENCES ............................................................................................................. 24 2 EXPERIMENTAL DETERMINATION OF SOLVENT–WATER PARTITION COEFFICIENTS AND ABRAHAM PARAMETERS FOR MUNITION CONSTITUENTS ............................................................................................. 25 2.1 Introduction .............................................................................................. 25 2.1.1 Polyparameter Linear Free Energy Relationships (pp-LFERs) ... 28 i 2.1.2 Octanol-Water Partition Coefficient ............................................ 29 2.2 Materials and Methods ............................................................................. 29 2.2.1 Materials ...................................................................................... 29 2.2.2 Selection of Solvent-Water Partitioning Systems ........................ 30 2.2.3 Experimental Methods ................................................................. 30 2.2.4 Determination of Abraham Solute Parameters ............................ 31 2.2.4.1 McGowan Characteristic Volume (V) .......................... 31 2.2.4.2 Excess Molar Refraction (E) ......................................... 31 2.2.4.3 Dipolarity/Polarizability (S), Hydrogen-Bond Acidity (A), and Hydrogen-Bond Basicity (B) ........................................ 32 2.3 Results and Discussion ............................................................................ 32 2.3.1 Validation of Experiment Results ................................................ 32 2.3.2 Analysis of Experiment Results ................................................... 33 2.3.3 Correlation of Partition Coefficients ............................................ 36 2.3.4 Analysis of the Experimentally Derived Abraham Parameters ... 36 2.3.5 Comparison of Solvent-Water Partition Coefficients between Experimental Measurements and Model Predictions .................. 38 2.3.6 Comparison of Physico-Chemical Properties between Experimental Measurements and Model Predictions ......................................... 40 2.4 Summary and Conclusions ...................................................................... 42 A SUPPLEMENTARY INFORMATION FOR: EXPERIMENTAL DETERMINATION OF SOLVENT–WATER PARTITION COEFFICIENTS AND ABRAHAM PARAMETERS FOR MUNITION CONSTITUENTS ................................... 48 3 QUANTUM CHEMICALLY ESTIMATED ABRAHAM SOLUTE PARAMETERS USING MULTIPLE SOLVENT-WATER PARTITION COEFFICIENTS AND MOLECULAR POLARIZABILITY ................................................................ 61 3.1 Introduction .............................................................................................. 61 3.2 Materials and Methods ............................................................................. 64 3.2.1 Data Compilation ......................................................................... 64 3.2.2 Estimating E ................................................................................. 65 3.2.3 Determining S, A, and B ............................................................... 66 3.3 Results and Discussion ............................................................................ 67 3.3.1 Determining E Independently ...................................................... 67 3.3.2 Comparisons between ABSOLV and QCAP for Various Solvent-Water Systems ........................................................................................ 68 ii 3.3.3 Comparisons between ABSOLV and QCAP for Munition Constituents and Munition-like Compounds .................................................... 69 3.3.4 Adjusted Quantum Chemically Estimated Abraham Parameters (Adjusted QCAP).......................................................................................... 70 3.3.5 Comparison of QCAP and Adjusted QCAP ................................ 73 3.3.6 Comparisons between ABSOLV, QCAP, and Adjusted QCAP for Various Solvent-Water Systems .................................................. 73 3.3.7 Comparisons between ABSOLV, QCAP, and Adjusted QCAP for Munition Constituents and Munition-like Compounds ............... 74 3.3.8 Comparison of Adjusted QCAP and COSMOments ................... 75 3.4 Conclusions .............................................................................................. 77 REFERENCES ............................................................................................................. 78 B SUPPLEMENTARY INFORMATION FOR: QUANTUM CHEMICAL ESTIMATED ABRAHAM SOLUTE PARAMETERS USING MULTIPLE SOLVENT-WATER PARTITION COEFFICIENTS AND MOLECULAR POLARIZABILITY .......................................................................................... 85 C QUANTUM CHEMICAL ESTIMATED ABRAHAM SOLUTE PARAMETERS USING MULTIPLE SOLVENT-WATER PARTITION COEFFICIENTS AND MOLECULAR POLARIZABILITY: SUPPLEMENTARY INFORMATION87 REFERENCES ........................................................................................................... 108 4 QUANTUM CHEMICALLY ESTIMATED ABRAHAM SOLUTE AND SYSTEM PARAMETERS FOR SOLVENT-WATER AND PLANT CUTICLE-WATER PARTITION COEFFICIENTS ....................................................................... 109 4.1 Introduction ............................................................................................ 109 4.2 Materials and Methods ........................................................................... 111 4.2.1 Partition Coefficient Data .......................................................... 111 4.2.2 Determination of System Parameters using Estimated Solute Parameters .................................................................................................... 111 4.3 Results and Discussion .......................................................................... 112 4.3.1 Analysis of the Refitted Models for Solvent-Water Systems .... 112 4.3.2 Comparison of the Original and Refitted Models for Solvent-Water Systems .....................................................................................