Arsenic and Chromium Speciation of Leachates …

1 I Arsenic and Chromium Speciation of Leachates from CCA-Treated Wood (FINAL) Submitted September 27, 2004 Helena Solo-Gabriele, , Bernine Khan, University of Miami, Coral Gables, FL Timothy Townsend, , Jin-Kun Song, Jenna Jambeck, Brajesh Dubey, Yong-Chul Jang, University of Florida, Gainesville, FL Yong Cai, Florida International University Miami, FL State University System of Florida FLORIDA CENTER FOR SOLID AND HAZARDOUS WASTE MANAGEMENT 2207 NW 13 Street, Suite D Gainesville, FL 32609 Report #03-07 ii This page left intentionally blank. This document is formatted for 2-sided TABLE OF CONTENTS TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES LIST OF ABBREVIATIONS AND ACRONYMS UNITS OF MEASURE ABSTRACT iii v viii xi xiii xiv CHAPTER I, BACKGROUND, MOTIVATION, AND OBJECTIVES Motivation 3 Background 3 Objectives 10 CHAPTER II, LABORATORY ANALYTICAL METHODS Arsenic Analysis of Liquid Leachates 13 Chromium Analysis of Liquid Leachates 17 Metal Analysis in Solid Samples 18 CHAPTER III, RESULTS FROM pH STAT EXPERIMENTS Sample Preparation 25 Results 26 CHAPTER IV.

2 RESULTS FROM TCLP AND SPLP FOR UNBURNED WOOD AND CCA-TREATED WOOD ASH Sample Descriptions and Pre-processing 37 Sample Processing for SPLP and TCLP Analysis 42 Results from Unburned CCA-Treated Wood 44 Results from CCA-Treated Wood Ash 49 Comparison Between SPLP and TCLP Tests and Between Unburned CCA- Treated Wood and CCA-Treated Wood Ash 56 iv TABLE OF CONTENTS (Con d) CHAPTER V, LYSIMETER STUDY Lysimeter Construction 63 Operation and Monitoring of Lysimeters 68 Results 69 CHAPTER VI, ANALYSIS OF GROUNDWATER NEAR C&D DEBRIS DISPOSAL FACILITIES Preliminary Efforts 81 New Strategy 82 Results 83 CHAPTER VII, SUMMARY, CONCLUSIONS, RECOMMENDATIONS, & ACKNOWLEDGMENTS Summary and Conclusions 91 Recommendations 94 Acknowledgments 95 REFERENCES 97 APPENDIX A: Separation of Arsenic Species by Ion-Exchange Cartridges 101 APPENDIX B: Data Log Sheet for Groundwater Sampling Study 109 APPENDIX C: Supplemental Data from Lysimeter Study 113 APPENDIX D.

3 Supplemental QA/QC Information 121 v LIST OF FIGURES Figure Eh-pH Diagram for Arsenic (Schnoor 1996) Figure Eh-pH Diagram for Chromium (Adapted from Ball and Nordstrom 1998) Figure Summary of Laboratory Methods Used for Arsenic Analysis for Liquid Leachates Figure HPLC-HG-AFS Setup Figure Chromatogram of the Four Major Arsenic Species using HPLC-HG-AFS Figure Summary of Laboratory Methods Used for Chromium Analysis of Liquid Leachates Figure Summary of Laboratory Methods Used for the Analysis of Solid Samples Figure Leaching of Arsenic from New Wood at Varying pH Values, Total Arsenic as Measured by AFS is in the Form of As(V) Figure Leaching of Chromium from New Wood at Varying pH Values Figure Leaching of Arsenic from Weathered Wood at Different pH Values Figure Leaching of Chromium from Weathered Wood at Different pH Values Figure Total Arsenic Concentrations for New and Weathered CCA-treated Wood Across the pH Range (HPLC-HG-AFS Analysis Method) Figure Distribution of Arsenic Among As(V) and As(III) Across the pH Range for Weathered Wood Figure Total Chromium Concentrations for New and Weathered CCA-treated Wood Across the pH Range Figure Distribution of Chromium Among Cr(III) and Cr(VI) Across the pH Range for Weathered Wood Figure Layout of the TCLP and SPLP Experiments Figure Processing Steps for the TCLP/SPLP Experiments vi LIST OF FIGURES (con d)

4 Figure Arsenic Species Observed In SPLP Leachates From Unburned Wood Samples Figure Chromium Species Observed In SPLP Leachates From Unburned Wood Samples Figure Arsenic Species Observed In TCLP Leachates From Unburned Wood Samples Figure Arsenic Species Observed In SPLP Leachates From CCA-Treated Wood Ash Figure Chromium Species Observed In SPLP Leachates From CCA-Treated Wood Ash Figure Chromium Concentration Versus Final pH of Leaching Solution for SPLP Leachates From CCA-Treated Wood Ash Figure Arsenic Species Observed In TCLP Leachates From CCA-Treated Wood Ash Figure Chromium Species Observed In TCLP Leachates From CCA-Treated Wood Ash Figure Comparison of Arsenic Species in Unburned Wood Between between the TCLP and SPLP Tests Figure Comparison of Arsenic Species in CCA-Treated Wood Ash Between between the TCLP and SPLP Tests Figure Chromium Concentrations in Unburned Wood As Observed During the SPLP Test Figure Comparison of Cr(VI) Concentrations in CCA-Treated Wood Ash Between between the TCLP and SPLP Tests Figure Schematic of Lysimeter Figure Comparison to Cumulative Total Arsenic Between Each Set of Lysimeters Using Data from HPLC-ICP-MS Analysis Figure Cumulative Quantities of Various Arsenic Species from Lysimeter 1 Figure Cumulative Quantities of Various Arsenic Species from Lysimeter 2 Figure Cumulative Quantities of Various Arsenic Species from Lysimeter 3 Figure Cumulative Quantities of Various Arsenic Species from Lysimeter 4 vii LIST OF FIGURES (con d)

5 Figure Cumulative Quantities of Various Arsenic Species from Lysimeter 5 Figure Cumulative Quantities of Various Arsenic Species from Lysimeter 6 Figure Total Arsenic for Background Wells as Measured by HPLC-ICP-MS and Independent Commercial Laboratories Figure Total Arsenic for Compliance/Detection Wells as Measured by HPLC-ICP-MS and Independent Commercial Laboratories Figure Arsenic Species of Compliance/Detection Wells that Tested Above Detection Limits Figure Ion-exchange Cartridge in Series Figure Fractional Concentrations of Arsenic Species Plotted as a Function of pH (Korte and Fernando, 1991) Figure Outline of the Cation-Exchange Cartridge Experiment Figure Outline of the Anion-Exchange Cartridge Experiment viii LIST OF TABLES Table Formulas of the Principal Arsenic Compounds (Benramdane et al. 1999) Table Formulas of Typical Chromium Compounds Table Experimental Conditions for Arsenic Speciation by HPLC-HG-AFS System Table Experimental Conditions for Cr(VI)

6 Analysis Using Ion Chromatography Table Results from the Analysis of the Solid Sawdust Samples Used in pH Stat Tests Table Leaching of Arsenic and Chromium from New Wood at Varying pH Values Table Leaching of Arsenic and Chromium from Weathered Wood at Varying pH Values Table Samples Utilized for TCLP and SPLP Analysis Table Measured Retention Level of the Outer 6/10 of the Unburned Wood Samples Used in TCLP and SPLP Experiments Table Metals Concentrations of Unburned Wood Samples Used in TCLP and SPLP Experiments Table Metals Concentrations of Solid Ash Samples Used in TCLP and SPLP Experiments Table SPLP Results for Unburned Wood Table TCLP Results for Unburned Wood Table SPLP Results for CCA-Treated Wood Ash Table TCLP Results for CCA-Treated Wood Ash Table Summary of Wood Types Contained Within Each Lysimeter Table Layers of Each Lysimeter Table Composition of Wood Monofill Lysimeters Table Composition of C&D Lysimeters ix LIST OF TABLES (Con d) Table SPLP Results for Unburned Wood Table TCLP Results for Unburned Wood Table SPLP Results for CCA-Treated Wood Ash Table TCLP Results for CCA-Treated Wood Ash Table Summary of Wood Types Contained Within Each Lysimeter Table Layers of Each Lysimeter Table Composition of Wood Monofill Lysimeters Table Composition of C&D Lysimeters Table Composition of MSW Lysimeters Table Average Total Arsenic Concentrations From Each Lysimeter Table Arsenic Results for Lysimeters 1 & 2 (Monofills) Table Arsenic Results for Lysimeters 3 & 4 (Simulated C&D) Table Arsenic Results for Lysimeters 5 & 6 (MSW)

7 Table Groundwater Data for Background Wells at C&D Debris Disposal Facilities Table Groundwater Data for Detection/Compliance Wells at C&D Debris Disposal Facilities Table Percent Recovery of Arsenic Species from Experiments with Ion-Exchange Cartridges Table Results for Lysimeter 1 (Monofill no CCA) Table Results for Lysimeter 2 (Monofill with CCA) Table Results for Lysimeter 3 (C&D Untreated Wood Only) Table Results for Lysimeter 4 (C&D With CCA-Treated Wood) Table Results for Lysimeter 5 (MSW Untreated Wood Added) Table Results for Lysimeter 6 (C&D With CCA-Treated Wood Added) x LIST OF TABLES (Con d) Table Methods Employed for Analyses that have been Standardized by Regulatory/Standardization Agencies Table Methods Employed for Analysis which are Utilized by the Research CommunityTable Reproducibility of Lysimeter Leachate Results Based Upon Duplicate Acid Digestion and Analysis Table Results from Spike Analysis on Samples from the pH stat Experiments Table Results from Spike Analysis for Total Chromium in CCA-treated Wood and CCA-treated Wood Ash Table Matrix Spike Recoveries for the Lysimeter Samples Table Results for CrVI Spike Analysis on CCA-treated Wood & Ash xi LIST OF ABBREVIATIONS AND ACRONYMS AES Atomic Emission Spectrometry AFS Atomic Fluorescence Spectroscopy As Arsenic As(III) Trivalent Arsenic , Arsenite As(V)

8 Pentavalent Arsenic , Arsenate AsB Arsenobetaine AsC Arsenocholine Ave. Average AWPA American Wood Preservers Association AWPI American Wood Preservers Institute BDL Below Detection Limit CCA Chromated Copper Arsenate C&D Construction and Demolition Cr Chromium Cr(III) Trivalent Chromium Cr(VI) Hexavalent Chromium Cu Copper DMAA Dimethylarsinic Acid DO Dissolved Oxygen Eh Measure of the Oxidation and Reduction Potential of A Solution FDEP Florida Department of Environmental Protection FIU Florida International University FPL Florida Power and Light GW Groundwater HG Hydride Generation HPLC High Performance Liquid Chromatography HPLC-HG-AFS High Performance Liquid Chromatography coupledwith Hydride Generation and Atomic FluorescenceSpectrometry HPLC-ICP-MS High Performance Liquid Chromatography coupledwith Inductively Coupled Plasma Mass Spectrometry xii LIST OF ABBREVIATIONS

9 AND ACRONYMS (Con d) IC Ion Chromatography ICP Inductively Coupled Plasma ICP-AES Inductively Coupled Plasma-Atomic Emission Spectrometry ICP-MS Inductively Coupled Plasma - Mass Spectrometry MDL Minimum Detection Limit LMAC Minnesota s Listed Metals Advisory Council MMAA Monomethylarsonic Acid MPCA Minnesota Pollution Control Agency MS Mass Spectrometry MSW Municipal Solid Waste NA Not Analyzed NS Not Sampled ORP Oxidation Reduction Potential pcf Pounds per Cubic Foot pH Measure of the hydrogen ion activity in water. Measure of the acidity of water. RCRA Resource Conservation and Recovery Act RDF Refuse Derived Fuel SPLP Synthetic Precipitation Leaching Procedure Std.

10 Dev. Standard Deviation SWA Solid Waste Authority SYP Southern Yellow Pine TAG Technical Awareness Group TCLP Toxicity Characteristic Leaching Procedure TMAO Trimethylarsine Oxide UF University of Florida UM University of Miami USEPA Environmental Protection Agency XRF X-ray fluorescence spectroscopy xiii UNITS OF MEASURE Inches % Parts Per Hundred, Percent ug Micrograms ug/L Micrograms Per Liter um Micron (1 millionth of a meter) oC Degrees Celcius cm Centimeters oF Degrees Farenheit ft3 Cubic Feet g Grams L Liter lb/ft3 Pounds Per Cubic Foot LD50 A measure of toxicity. Lethal dose at which 50% of the test population dies.