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ABSTRACT TRACING HYDROCARBON CONTAMINATION THROUGH HYPERALKALINE ENVIRONMENTS IN THE CALUMET REGION OF SOUTHEASTERN CHICAGO Kathryn Quesnell, MS Department of Geology and Environmental Geosciences Northern Illinois University, 2016 Melissa Lenczewski, Director The Calumet region of Southeastern Chicago was once known for industrialization, which left pollution as its legacy. Disposal of slag and other industrial wastes occurred in nearby wetlands in attempt to create areas suitable for future development. The waste creates an unpredictable, heterogeneous geology and a unique hyperalkaline environment. Upgradient to the field site is a former coking facility, where coke, creosote, and coal weather openly on the ground. Hydrocarbons weather into characteristic polycyclic aromatic hydrocarbons (PAHs), which can be used to create a fingerprint and correlate them to their original parent compound. This investigation identified PAHs present in the nearby surface and groundwaters through use of gas chromatography/mass spectrometry (GC/MS), as well as investigated the relationship between the alkaline environment and the organic contamination. PAH ratio analysis suggests that the organic contamination is not mobile in the groundwater, and instead originated from the air. 16S rDNA profiling suggests that some microbial communities are influenced more by pH, and some are influenced more by the hydrocarbon pollution. BIOLOG Ecoplates revealed that most communities have the ability to metabolize ring structures similar to the shape of PAHs. Analysis with bioinformatics using PICRUSt demonstrates that each community has microbes thought to be capable of hydrocarbon utilization. The field site, as well as nearby areas, are targets for habitat remediation and recreational development. In order for these remediation efforts to be successful, it is vital to understand the geochemistry, weathering, microbiology, and distribution of known contaminants. Many PAHs are toxic in both the environment and to humans, and are known to be both carcinogenic as well as bioaccumulate. Thus, understanding the relationship of PAHs to the geochemistry of this field site provides critical information for ongoing research and future remediation efforts. NORTHERN ILLINOIS UNIVERSITY DE KALB, ILLINOIS AUGUST 2016 TRACING HYDROCARBON CONTAMINATION THROUGH HYPERALKALINE ENVIRONMENTS IN THE CALUMET REGION OF SOUTHEASTERN CHICAGO BY KATHRYN ANN QUESNELL © 2016 Kathryn Ann Quesnell A THESIS SUBMITTED TO THE GRADUATE SCHOOL IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE MASTER OF SCIENCE DEPARTMENT OF GEOLOGY AND ENVIRONMENTAL GEOSCIENCES Thesis Director: Melissa E. Lenczewski ACKNOWLEDGEMENTS There are far too many people to thank for the creation of this project. For their aid in funding this project, I would like to thank the Illinois Groundwater Association and the Geological Society of America for their generous support. From Northern Illinois University, I would like to thank NIU Department of Geology and Environmental Geosciences’ Samuel Goldich Fund, The NIU Graduate School’s Travel Fund and the College of Liberal Arts and Sciences for further funding my research. For funding me, personally, I would like to thank the family of Brian Fugiel for their generous scholarship through the department, as well as The Institute for the Study of the Environment, Sustainability, and Energy/Environmental Studies. For his generous donation of time and lab analysis, I would like to thank Stan Zaworski at First Environmental Laboratories in Naperville, Illinois. For laboratory support, I would like to thank Monica Carroll, Ellen Raimondi, and the Swingley Lab. Finally, I would like to thank my thesis committee, Melissa Lenczewski, Wes Swingley, and Philip Carpenter for their patience and understanding in the face of every small project- related emergency. DEDICATION To my parents, for supporting me, and, more importantly, for never questioning me on this crazy journey. TABLE OF CONTENTS LIST OF TABLES………………………………………………..…………...………............…vi LIST OF FIGURES…………………………………………………………………….…….....vii LIST OF APPENDICES……………………..……………………………………………….…viii Chapter 1. INTRODUCTION ......................................................................................................................1 2. BACKGROUND ........................................................................................................................3 History of the Calumet Region……………………………………………………………3 Modern Field Site…………………………………………………………………………5 PAHS and the Environment……………………………………………………………….7 Alkaline Environments…………………………………………………………………..10 Field Methods of Investigation…………………………………………………………..11 3. MATERIALS AND METHODS ..............................................................................................13 Sampling Periods……………………………………………...…………………………13 Field Sampling Methods…………………………………………………………………13 Organic Chemistry: PAH Analysis……………………………………………………….15 Aqueous Geochemistry…………………………………………………………………..15 Biological Filtration and 16S rDNA Sequencing…………………………………………16 BIOLOG Ecoplates………………………………………………………………………17 4. DATA ANALYSIS AND DISCUSSION……………………………………………………..19 Inorganic Chemistry……...………………………………………………………………19 v Organic Geochemistry…………………………………………………………………...21 Biology…………………………………………………………………………………...28 5. CONCLUSION………………………………...……………………………………………...42 REFERENCES…………………………………………………………………………………..44 APPENDICES…………………………………………………………………………………...50 LIST OF TABLES Page Table 2.1 16 EPA Priority Pollutants……...………………………………………….……………9 Table 3.1 Collected Field Samples Summary……………...........…………………….………….14 Table 4.1 Summer Water Sample Inorganic Characterization (8/18/2014)…………..……......…19 Table 4.2 Winter Water Sample Inorganic Characterization (12/16/2014)………….........………21 Table 4.3 Summer 16 EPA PAH Priority Pollutant Data (8/18/2014)…………………..……......22 Table 4.4 Winter 16 EPA PAH Priority Pollutant Data (12/16/2014)……………………..……...23 Table 4.5 Summer PAH Pearson Coefficients (12/16/2014)…….……………………………….24 Table 4.6 Winter PAH Pearson Coefficients (8/18/2014)………………………………………...24 Table 4.7 16 EPA Priority Pollutant Mobility…………………………………………………….28 Table 4.8 Structure of BIOLOG Carbon Substrates………………………………………………29 Table 4.9 Total PAHS of Selected Sites………………………………………………………….33 Table 4.10 Diversity Indices (from Class Data)…………………………………………………..38 Table 4.11 PICRUSt PAH KEGG Pathways One-Sample T-test………………………………...40 LIST OF FIGURES Page Figure 2.1 Overview of the Area of Investigation…………………………………………………5 Figure 2.2 Overview of Big Marsh Transect……………….....……………………………………6 Figure 2.3 Overview of the Slag Dunes and Wolf Lake Comparison Site ………………..……......7 Figure 4.1 FL/PY to PH/AN Ratios of Select Calumet Samples Compared to Known Sources......26 Figure 4.2 BIOLOG Total Microbial Growth……………………………………………………30 Figure 4.3 pH Related to Microbial Growth……………………………………………………...31 Figure 4.4 BIOLOG PCA Data…………………………………………………………………...32 Figure 4.5 BIOLOG Carbon Structure Utilization………………………………………………..33 Figure 4.6 Summer 16S rDNA Microbial Profiles by Class……………………………………...34 Figure 4.7 16S rDNA Profiles PCA………………………………………………………………37 Figure 4.8 PAH-Related KEGG Pathways………………………………………………….……39 Figure 4.9 Hydrocarbon Degradation KEGG Pathways Related to Total PAHs………………….41 LIST OF APPENDICES Appendix Page A. 16S RDNA DATA…………………………………………………...………………………..50 B. 16S RDNA PCA DATA……………………………………………..………………………113 C. PCA DATA BIOLOGS……………………………………………………………………..116 D. PICRUST DATA……………………………………………………………………………119 E. BIOLOG DATA……………………………...……………………………………………..139 CHAPTER 1 INTRODUCTION The Calumet region of Southeastern Chicago archives its industrial legacy in pollution. Slag waste and garbage were used to fill marshes to make land suitable for residential and industrial development (Colton, 1986). Previous research of the area explored chemical reactions caused by the interaction of meteoric water and slag waste, creating the hyperalkaline conditions up to pH 13.4 of the ground and surface waters of the area (Roadcap et al., 2005; Roadcap et al., 2006). Immediately surrounding the hyperalkaline waters is an Army Corps of Engineers habitat restoration project, where species such as the Black Crowned Night Heron (endangered in the state of Illinois) live. The field site itself is being converted by the Chicago Park District into bike trails. Landfills in the area formerly produced leachate springs near the area of investigation (Waska, 2014). The former property of Acme Steel (later Acme Coke) has coke, creosote, and coal lying openly and weathering on the ground. Waska (2014) focused on characterization of groundwater flow paths, site-dependent microbial community characterization based on geochemistry, and hyperalkaline water remediation methods. However, in his investigation, he also noted unknown organic contamination present in both surface and groundwaters, but did not pursue investigation of the contamination further. 2 The purpose of this research is to characterize the organic contamination discovered in previous studies, and determine if the contamination is linked to the exposed hydrocarbons on the former Acme Coke Facility. Additionally, the microbial communities and their relationship with the organic contamination will be investigated. CHAPTER 2 BACKGROUND History of the Calumet Region The natural surface and near-surface geology of the Calumet region is the result of previous glaciation. Although the area was believed to have 20-30 feet of Illinoian Stage drift,