CHARACTERIZATION AND NEUTRALIZATION OF ARSENICAL-BASED

10,3

MB

WWII ERA CHEMICAL MUNITION FILLS

216

stron

3576

ID

EAI Corporation

2006

rok

CONTENTS

1. INTRODUCTION . 1

1.1 Background .. 1

1.2 Study Objectives . 5

2. EXPERIM ENTAL PROCEDURES 5

2.1 M icro-Scale Reaction Studies .. 6

2.2 Sm all-Scale Lab Reaction Studies 6

2.3 Large-Scale Lab Reaction Studies 7

2.4 Standards . 7

2.5 Residual Agent M ethod .. 8

2.5.1 Optim ization Experim ents . 8

2.5.2 Calibration M odel . 9

2.5.3 M ethod Precision and Accuracy .. 15

2.5.4 M ethod Detection Limit . 17

2.6 Reaction Product M ethod 18

2.6.1 Instrum entation .. 18

2.6.2 Reagents 19

2.6.3 Targeted Analytes . 19

2.6.4 Procedure .. 19

2.7 Determination of Residual Perm anganate .. 23

3. RESULTS AND DISCUSSION . 25

3.1 Identification of Fill Components . 25

3.1.1 Qualitative Gas Chrom atographic Experim ents .. 26

3.1.2 Qualitative NM R Experim ents . 31

3.2 Quantitation of Fill Components 32

3.2.1 Bulk Composition by NM R 32

3.2.2 W ater Soluble Products . 45

3.2.3 Total M etals . 46

3.2.4 Bulk Density of Fill M ateriels . 48

3.3 Selection of Neutralization Reagent .. 48

3.3.1 M icro-Scale Screening of Reagent Candidates 48

3.3.2 Sm all-Scale Screening of Reagent Candidates . 53

3.3.3 Initial Investigations into the Efficacy of Sodium Permanganate 56

3.4 Preparation and Characterization of Permanganate Reagent . 57

3.4.1 General Properties of Perm anganate Reagent .. 57

3.4.2 M aterials Com patibility 59

3.4.3 Reaction M echanism 61

3.5 Small-Scale Laboratory Demonstration of Permanganate Reagent 67

3.5.1 Reaction Conditions .. 67

3.5.2 Temperature Profiles and Observations 69

3.5.3 Residual Agents 74

3.5.4 Quantitation of Reaction Products .. 80

3.5.5 Isolation and Characterization of Solids from Small-Scale Runs 90

3.5.6 Composition of Isolated Solids as a Function of Reaction and Storage Times . 94

3.6 Large-Scale Dem onstration of Perm anganate Reagent . 110

3.6.1 Reaction Conditions 110

3.6.2 Temperature Profiles and Observations 111

3.6.3 Residual Agents 111

3.6.4 Neutralent Storage Study . 114

3.6.5 RCRA W aste Characterization . 121

3.6.6 M aterials Compatibility 124

3.7 Full-Scale Validation of Perm anganate Reagent . 133

3.7.1 Reaction Conditions 133

3.7.2 Residual Agents 134

3.7.3 Quantitation of Reaction Products .. 135

3.7.4 Total M etals 152

3.7.5 Qualitative Analyses by NM R and LC/M S . 155

3.7.6 Residual Sodium Perm anganate .. 156

3.7.7 Isolation and Characterization of Solids from Waste and Sludge Samples . 15 6

4. CONCLUSIONS .. 176

LITERATURE CITED . 177

APPENDIX - RESIDUAL AGENT METHOD DESCRIPTION IN SOP FORM AT .. 187