Synthesis of Iron Oxide Pigment from the Treatment of Truetown Acid Mine Drainage Utilizing Aeration A thesis presented to the faculty of the Russ College of Engineering and Technology of Ohio University In partial fulfillment of the requirements for the degree Master of Science Alexander P. Doksa May 2015 © 2015 Alexander P. Doksa. All Rights Reserved. 2 This thesis titled Synthesis of Iron Oxide Pigment from the Treatment of Truetown Acid Mine Drainage Utilizing Aeration by ALEXANDER P. DOKSA has been approved for the Department of Civil Enigneering and the Russ College of Engineering and Technology by R. Guy Riefler Professor of Civil Engineering Dennis Irwin Dean, Russ College of Engineering and Technology 3 Abstract DOKSA, ALEXANDER P., M.S., May 2015, Civil Engineering Synthesis of Iron Oxide Pigment from the Treatment of Truetown Acid Mine Drainage Utilizing Aeration Director of Thesis: Guy Riefler In recent centuries, mining for metals and fossil fuels has caused numerous water sources to become heavily polluted. Coal mining, specifically in the Appalachian region, has scarred the land with mines, and has painted the affected waterways orange with acid mine drainage (AMD). The objective of this thesis was to investigate a precipitation pigment production process to remediate the Truetown AMD seep while producing a marketable IOP. The manipulation and control of variables such as pH, temperature, seed, and water chemistry played an important role in goethite pigment production. The production and pigment quality testing as completed in this research indicates that goethite (α-FeOOH) pigments can be produced from Truetown AMD at qualities comparable to commercial grade pigments with respect to ferric oxide content, hiding power, and coloration. The preferred oxidation pH values were acidic, as it was observed to produce an overall higher quality goethite pigment. Ferrous iron reaction rates were observed to increase with higher oxidation pH values and temperature. The Rublev lemon ocher used in this research as seed was not compositionally similar to goethite and was an ineffective tool in the development of goethite pigment from AMD. When comparing the ferric oxide contents of pigments produced from lab grade ferrous sulfate salt to Truetown AMD, they were determined to be statistically equal. However, the higher ferrous iron and sulfate concentrations of the lab tests were 4 observed to have negatively affected the goethite crystal structure, and subsequently caused the produced drawdowns to be darker in color. 5 Acknowledgements I am thankful for having had the opportunity to work on this project and contribute in a small part to the continued research and development of acid mine drainage remediation systems. I would like to thank Dr. Guy Riefler for his guidance, wisdom, and patience through the entirety of this project. I would also like to thank my graduate committee members; Dr. Ben Stuart, Dr. Natalie Kruse, and Dr. John Sabraw. 6 Table of Contents Page Abstract ............................................................................................................................................ 2 Acknowledgements.......................................................................................................................... 5 List of Tables .................................................................................................................................... 8 List of Figures ................................................................................................................................. 10 Chapter 1: Introduction ................................................................................................................. 13 1.1 Acid Mine Drainage ............................................................................................................. 13 1.2 Acid Mine Drainage Treatment .......................................................................................... 16 1.3 Pigments and Color ............................................................................................................. 20 1.4 Iron Oxide Pigments ............................................................................................................ 21 1.5 Iron Oxide Pigment Production ........................................................................................... 22 1.6 Objectives ............................................................................................................................ 25 Chapter 2: Materials and Methods ................................................................................................ 27 2.1 Sample Collection ................................................................................................................ 27 2.2 Pigment Synthesis............................................................................................................... 28 2.3 Testing Plan ......................................................................................................................... 31 2.4 Kinetics ................................................................................................................................ 33 2.5 Pigment Analysis .................................................................................................................. 34 2.5.1 Ferric Oxide Content ........................................................................................................ 35 2.5.2 Powdered X-Ray Diffraction .............................................................................................. 37 2.5.3 Drawdowns ....................................................................................................................... 38 2.6 Individual Ion Effects on Ferric Oxide Content .................................................................... 41 7 Chapter 3: Results .......................................................................................................................... 42 3.1 Kinetics ................................................................................................................................ 42 3.2 Ferric Oxide Content of Synthesized Pigment ..................................................................... 48 3.3 Individual Ion Effects on Ferric Oxide Content .................................................................... 50 3.4 Powdered X-Ray Diffraction Data ........................................................................................ 53 3.5 Drawdowns........................................................................................................................... 59 Chapter 4: Discussion ........................................................................................................... 67 4.1 The Affect of Seeding and Source Water on Ferric Oxide Content ..................................... 67 4.2 Pigment Synthesis pH and Ferric Oxide Content ................................................................ 70 4.3 Kinetics with respect to Oxidation pH ................................................................................. 78 4.4 Synthesis pH and its Impacts on Pigment Synthesis ........................................................... 82 4.5 Effect of pH, Source Water, and Seed on Goethite Crystal Structure ................................. 82 4.6 Effects of Individual Ions on Ferric Oxide Content .............................................................. 85 4.7 Pigments and Hiding Power ................................................................................................ 87 4.8 Drawdown Color, pH, and Goethite Crystal Structure ........................................................ 88 Chapter 5: Conclusion and Recomendations ................................................................................. 90 References ..................................................................................................................................... 92 Appendix A: Intial pH and Dissolved Iron Data .............................................................................. 95 Appendix B: Plotted Dissolved Iron Data ....................................................................................... 96 Appendix C: Drawdowns .............................................................................................................. 106 8 List of Tables Page Table 1.1: Average water quality data of the Truetown AMD seep 2000-2011 ......................... 15 Table 2.1: Pigment synthesis tests performed ........................................................................... 32 Table 2.2: Rate laws for zero, first and second order reactions ................................................. 33 Table 3.1: Raw data from the TT Unseeded 3.5 aeration test .................................................... 42 Table 3.2: Calculated reaction orders for the listed aeration tests ............................................ 45 Table 3.3: Reaction rates for the listed aeration tests................................................................ 47 Table 3.4: Ferric oxide data from the ASTM D 50-90 testing method ........................................ 49 Table 3.5: The initial and final pH for each ion profile test ........................................................ 50 Table 3.6: Ion concentration for ferrous iron, sulfate, sodium and hydroxide per ion profile test 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