The Removal of Barium, Strontium, Calcium and Magnesium from Hydraulic Fracturing

Home , Barium, Produced water, Strontium, Strontium carbonate, Strontium sulfate

Produced Water Using Precipitation with Traditional and Alternative Reactant

Feedstocks

A thesis presented to

the faculty of

the Voinovich School of Leadership & Public Affairs

In partial fulfillment

of the requirements for the degree

Master of Science

Jess D. Cogan

April 2016

The Removal of Barium, Strontium, Calcium and Magnesium from Hydraulic Fracturing

Produced Water Using Precipitation with Traditional and Alternative Reactant

Feedstocks

JESS D. COGAN

has been approved for

the Program of Environmental Studies

and the Voinovich School of Leadership & Public Affairs by

Natalie A. Kruse Daniels

Associate Professor of Environmental Studies

Mark Weinberg

Director, Voinovich School of Leadership & Public Affairs 3 ABSTRACT

COGAN, JESS D., M.S., April 2016, Environmental Studies

The Removal of Barium, Strontium, Calcium and Magnesium from Hydraulic Fracturing

Produced Water Using Precipitation with Traditional and Alternative Reactant

Feedstocks

Director of Thesis: Natalie A. Kruse Daniels

Marcellus and Utica shale gas exploration is an industry that expands from southeastern New York, West Virginia, Pennsylvania and Ohio. The recovery of natural gas from the Marcellus and Utica shale beds is done through hydraulic fracturing.

Hydraulic fracturing is a process that pumps large amounts of water into the shale formation causing fractures, allowing the gas to flow to the surface. As the water returns to the surface it is contaminated with inorganic compound found within the shale formation. This water is characterized as produced and flowback water. This study tested the removal rates of Ba+2, Sr+2, Ca+2 and Mg+2 from four synthetic produced water solutions undergoing treatment. The treatments were sulfation to remove Ba+2, softening to remove Ca+2, and hydrolysis to remove Mg+2. Sr+2 was also removed from the synthetic produced water solutions, but was not treated for specifically. Strontium removal occurred through co-precipitation during barium, calcium and magnesium treatments. The treatment order was found to impact the removal efficiency of these constituents. The optimized treatment of sulfation - hydrolysis- softening resulted in a

97-100% removal of barium, 97-100% removal of magnesium, 84-100% removal of calcium, and 64-100% removal of strontium. Acid mine drainage treatment showed 4 efficient removal of barium from all four synthetic solutions ranging from 63-99% removal, but strontium removals were low ranging from 1-16% removal. 5 DEDICATION

This thesis is dedicated to my family, who instilled and supported my love for the

outdoors and the beauty it provides. 6 ACKNOWLEDGMENTS

A big thank you goes out to my advisor, Dr. Natalie Kruse for her utmost support and help through the research, writing, and completion of this project. I would like to thank my committee members Dr. Dina Lopez and Dr. Jason Trembly for their support and advisement. I would also like to thank the staff at the Institute for Sustainable Energy and the Environment, Shyler Switzer, David Ogden, Mira Cooper and Dr. Wen Fan for their cooperativeness and troubleshooting of the project hurdles, I would also like to thank Dr. Ben Stuart and Dr. Anirudh Ruhil for their help and advisement. I would like to thank my family for their support and the opportunity for this project provided to me by

Voinovich School of Leadership and Public Affairs. 7 TABLE OF CONTENTS

Page

Abstract ...... 3 Dedication ...... 5 Acknowledgments...... 6 List of Tables ...... 9 List of Figures ...... 10 Chapter 1: Introduction ...... 12 1.1 Objectives, Deliverables, Hypothesis ...... 14 Chapter 2: Literature Synthesis ...... 16 2.1 Produced Water Composition ...... 16 2.2 Environmental Health and Effects ...... 18 2.3 Naturally Occurring Radioactive material (NORM) ...... 20 2.4 Treatment and Disposal Methods ...... 21 2.5 Precipitation Treatment ...... 24 2.6 Acid Mine Drainage as a Possible Treatment Strategy ...... 24 Chapter 3: Methods ...... 27 3.1 Stock Solution Composition ...... 27 3.2 Equilibrium Studies ...... 28 3.2.1 Sulfation ...... 28 3.2.3 Hydrolysis ...... 30 3.2.3 Softening ...... 33 3.3 Kinetics ...... 35 3.4 Acid Mine Drainage Treatment ...... 36 Chapter 4: Results and Discussion ...... 39 4.1 Batch Experiments ...... 39 4.2 Kinetics ...... 49 4.3 Acid Mine Drainage Treatment ...... 60 Chapter 5: Conclusions ...... 68 5.1 Batch Experiments ...... 68 5.2 Kinetics ...... 69 8 5.3 Acid Mine Drainage Treatment ...... 69 References ...... 71 Appendix 1 – Batch Experiment Results and Summary Statistics ...... 76 Appendix 2 – Kinetics Results and Summary Statistics ...... 79 Appendix 3 – Acid Mine Drainage Treatment Results and Summary Statistics ...... 83 9 LIST OF TABLES

Page

Table 1: Produced Water Quality for Pennsylvania, Ohio and West Virginia ...... 17

Table 2: Alternative Treatment Method Costs ...... 23

Table 3: Targeted mg/L of Constituents In Stock Solutions...... 28

Table 4: Amount of Constituents Added to Stock Solutions...... 28

Table 5: Solution pH During Precipitation Treatments ...... 49

Table 6: Solution pH During AMD Treatments ...... 65 10 LIST OF FIGURES

Page

Figure 1. Flow Chart Followed for Sulfation Testing...... 30

Figure 2. Flow Chart Followed for Hydrolysis Testing...... 32

Figure 3. Flow Chart Followed for Softening Testing...... 35

Figure 4. Flow Chart Followed for Acid Mine Drainage Testing...... 38

Figure 5a and 5b. Low IC (0.5) Removal Results with Hydrolysis Stage 3 and Softening

Stage 3...... 41

Figure 6a and 6b. Medium IC (0.5) Removal Results with Hydrolysis Stage 3 and

Softening Stage 3...... 43

Figure 7a and 7b. High IC (2) Removal Results with Hydrolysis Stage 3 and Softening

Stage 3...... 45

Figure 8a and 8b. High IC (4) Removal Results with Hydrolysis Stage 3 and Softening

Stage 3...... 47

Figure 9a-9b. Optimization and Scoping Results From the Low IC (0.5) and High IC (4)

Sulfation Stage 1 Kinetics Trials ...... 51

Figure 10a and 10b. Optimization and Scoping Results From the Low IC (0.5) and High

IC (4) Hydrolysis Stage 2 Kinetics Trials...... 53

Figure 11a and 11b. Optimization and Scoping Results From the Low IC (0.5) and High

IC (4) Hydrolysis Stage 3 Kinetics Trials...... 54

Figure 12a and 12b. Optimization and Scoping Results From the Low IC (0.5) and High

IC (4) Softening Stage 2 Kinetics Trials...... 57 11 Figure 13a and 13b. Optimization and Scoping Results From the Low IC (0.5) and High

IC (4) Softening Stage 3 Kinetics Trials...... 58

Figure 14. Low IC (0.5) Removal Results with AMD As Sulfation Treatment...... 61

Figure 15. Medium IC (1) Removal Results with AMD As Sulfation Treatment...... 62

Figure 16. High IC (2) Removal Results with AMD As Sulfation Treatment ...... 63

Figure 17. High IC (4) Removal Results with AMD As Sulfation Treatment...... 64

Figure 18. Strontium vs. pH...... 66

12 CHAPTER 1: INTRODUCTION

Marcellus and Utica shale gas exploration is an industry that has expanded

immensely in recent years spanning from southeastern New York, West Virginia,

Pennsylvania and Ohio. Natural gas, oil, and natural gas liquids (NGLs) are all extracted

through the use of hydraulic fracturing (Thompson, 2012). Hydraulic fracturing is a

process that uses water, sand, and a chemical mixture injected at a high pressure to

fracture the shale releasing the gas. When the gas returns to the surface it also carries

with it water. This water returns to the surface in two forms, flowback, and produced

water. Flowback is water that returns to the surface before the well is producing natural

gas. Produced water is water that returns to the surface once the well is producing natural

gas (Ziemkiewicz et al., 2012). Flowback and produced waters generally contain

substantial concentrations of Ba+2, Sr+2, Mg+2, Fe+2, Mn+2, Ca+2, Ra+2, Cl- and Na+. This

water can also contain chemicals from the fracturing fluids such as: potassium chloride,

guar gum, ethylene glycol, sodium carbonate, potassium carbonate, sodium chloride,

borate salts, citric acid, glutaraldehyde, acid, petroleum, distillate, and isopropanol

(Rahm, 2011; Haluszczak et al., 2013). The concentrations of these constituents make the fluid a contaminated brine solution that can potentially be harmful to the environment.

This research project aims to treat the produced water through precipitation reactions for the removal of Ba2+, Sr2+, Mg2+, and Ca2+. Optimized doses of chemical will be used to

treat produced water based on the concentrations of these ions present, provident an

efficient form of treatment.

Energy extraction is resource intensive requiring energy, manpower, heavy

equipment, and water. Hydraulic fracturing operations typically require 3-5 million 13 gallons of water to fracture one well, and one operation could have multiple wells drilled from the same location (Arthur et al., 2010). Hydraulic fracturing is a necessary method for shale gas extraction because shale formations do not have enough permeability to allow sufficient flow of natural gas (Arthur et al., 2010). The Marcellus and Utica shale formations will account for 35% of domestic production by 2035 (Arthur et al., 2010).

This production requires large amounts of water, but usable water sources for the industry are becoming more difficult to acquire due to regulation, leasing, permitting, and raising awareness about possible water contamination related to hydraulic fracturing. Treating the produced water created by the industry is the best solution to the issue of water supply surrounding the industry.

Flowback water and produced water are the two wastewater sources produced during hydraulic fracturing. After fracturing 10-30% of the water injected into the well for fracturing returns to the surface in the form of these two sources (Ziemkiewicz et al.,

2012; Rahm et al., 2013; Rassenfoss, 2011). Flowback water is water that returns to the surface of the well between the fracturing process and the start of gas production.

Produced water is water that returns to the surface of the well when natural gas is being produced. Flowback and produced water contain naturally occurring constituents from within the shale formation.

The flowback wastewater is generally reused to fracture a subsequent well because it is very similar in composition to the initial fracturing fluid. Produced waters have more time to interact with the geological formations and are more contaminated with inorganic compounds and constituents found below ground (Ferrar et al., 2013).

Currently much of this produced water is being trucked to Ohio for deep well injection. 14 While deep well injection costs are around $0.40- $1.75 per barrel, this method of disposal is not cost effective, it costs roughly $100 per hour to haul produced water to these injection sites, depending on well location. The trucks can haul roughly 150 barrels of water and trucking costs add $2.00-$4.00 per barrel to the disposal cost of each barrel

(Rassenfoss, 2011; Tirreno, 2014; (Mondal & Wickramasinghe, 2008).

1.1 Objectives, Deliverables, Hypothesis

The objectives of this study are:

1. To determine amount of dosing agent to remove 90% or alternative sufficient

removal rate of Ba+2, Sr+2, Ca+2 and Mg+2.

Deliverable: Provide data with conclusive evidence that 90% or alternative

sufficient removal rate of Ba+2, Sr+2, Ca+2, and Mg+2 can be achieved.

Hypothesis: Dosing agent will remove targeted amounts of Ba+2, Sr+2, Ca+2,

and Mg+2 from solution based on a 1:1 molar ratio of dosing agent to targeted

cation.

2. To determine the reaction time of each equilibrium reaction.

Deliverable: Provide a reaction time that deems that equilibrium reactions

complete.

Hypothesis: Kinetics of reaction will be almost instantaneous, less than 30 s

3. To determine the effectiveness of AMD as a possible reactant feedstock for the

removal of Ba+2.

Deliverable: Determine if Acid Mine Drainage can effectively remove Ba+2

from solution, and provide a system to prescribe a specific amount of AMD to

treat a specific amount of Ba+2 in solution. 15 Hypothesis: Acid Mine Drainage will be a viable reactant feedstock for the removal of Ba+2 from solution, but will require a large volume for treatment.

16 CHAPTER 2: LITERATURE SYNTHESIS

2.1 Produced Water Composition

The range and high concentrations of chemicals present in produced water make it very difficult to dispose of and/ or treat effectively. There are three key components that make up shale gas wastewater: drilling mud, flowback, and produced brine. Each of these three occurs at different stages of the drilling, fracturing, and production process

(Rahm et al., 2013). Drilling muds are clay rich slurries that are used to lubricate and cool the drill bit during the drilling of a natural gas well. Flowback water is the largest wastewater stream by volume from hydraulic fracturing, and it is characterized as the water that returns to the surface during fracturing but before gas production. Flowback water is very close in composition to the fracturing water used to drill the well, in turn this water is generally stored and treated using filtration or precipitation techniques and reused in the industry (Barbot et al., 2013). Produced water is the water that returns to the surface after the start of gas production (Ziemkiewicz et al., 2012). Global estimates of produced water production are around 250 million barrels per day (Fakhru-Razi et al.,

2009). The abundance of this water combined with carrying of high levels of inorganic compounds (e.g. Cl-, Br2+, Na+, K+, Ca2+, Mg2+, Sr2+, Ba2+, Ra) and TDS values that

range from 10,000 to 300,000 mg/L make it a very unusable water source to the industry

(Rahm et al., 2013). Table 1 shows the summary of produced water quality from

Pennsylvania, Ohio, and West Virginia according to the U.S. Geological Surveys

produced water database (U.S. Geological Survey, 2015).

17 Table 1: Produced Water Quality from Pennsylvania, Ohio and West Virginia Wells Number of Minimum Maximum Average Samples TDS (mg/L) 26 528,724 148,145 2,303 TSS (mg/L) 2 5,290 288 112 COD (mg/L) 10 51,000 5,863 115 TOC (mg/L) 1.2 5,680 311 95 pH 1.2 11.8 6.26 1,028 -2 SO4 (mg/L) 0.01 3,910 237 1,630 Cl- (mg/L) 1 97,400 97,036 2,489 Alkalinity (mg/L as CaCO3) 13 1,235 189 8 Br- (mg/L) 0.01 2,129,000 2,374 1,849 Na+ (mg/L) 0.2 434,403 36,965 2,448 Ca+2 (mg/L) 0.4 101,200 17,510 2,461 Mn+2 (mg/L) 0.002 138 26 941 Mg+2 (mg/L) 0.4 137,110 2,710 2,457 Ba+2 (mg/L) 0.01 13,600 377 978 Sr+2 (mg/L) 0.009 13,100 736 124 Fe+2 Total (mg/L) 0.01 5,800 154 1,460 Ra226 (pCi/L) 0.08 5,300 244 53 Ra228 (pCi/L) 0.05 9.27 0.52 43

The water gains all of these dissolved constituents from both the addition of fracturing fluids and interaction with the shale formations where it is injected. The first constituents added to the water are fracturing fluids. The fracturing fluids that are added vary in composition but contain chemicals such as potassium chloride, guar gum, ethylene glycol, sodium carbonate, potassium carbonate, sodium chloride, borate salts, citric acid, glutaraldehyde, acid, petroleum, distillate, and isopropanol (Rahm, 2011).

These substances are added to the fracturing fluid to help prevent pipe corrosion, minimize friction, aid the fracking process, and prevent scaling on equipment (Rahm,

2011). The addition of these chemicals increases the longevity of the drilling equipment and reduces drilling costs. 18 The composition of produced water varies due to the different chemicals used in the drilling process, but also from the geological formation being developed. The

Marcellus Shale region forms the bottom of Devonian age sedimentary rocks in the

Appalachian Basin (Soeder & Kappel, 2009). This shale region was deposited as an organic rich mud which was compressed and heated, forming hydrocarbons. This is the origin of the majority of the organic constituents in the produced waters. It is important to understand that produced water composition is specific to the geological formations where the well has been fractured. A study conducted in Pennsylvania on produced water quality parameters noted that produced water from the Marcellus Shale had higher concentrations of Ba+2 than the formations in the Lower Silurian and Upper Devonian formations (Barbot et al., 2013; Viel et al., 2004). Produced water that has elevated concentrations of Ba2+, Ca2+, and Sr2+making it less desirable for reuse in the industry.

These compounds are scalers which cause corrosion on the piping and equipment used during the fracturing process, this scaling can lead to equipment failure (Barbot et al.,

2013).

2.2 Environmental Health and Effects

While hydraulic fracturing has been a means of resource extraction for years, there is controversy surrounding the environmental effects and potential health effects of fracturing operations. A study conducted by the Pennsylvania Department of

Environmental Protection and the Susquehanna River Basin Commission found that from the Material and Safety Data Sheets, 73% of the chemicals listed from fracturing operations had between 6 and 14 health effects. These effects ranged from sensory organ damage, cancers, reproductive effects, gastrointestinal and liver disease brain and 19 nervous system harms (Finkel & Law, 2011). The chemicals that specifically cause

concern are endocrine-disrupting chemicals that can have effects decades from the time

of exposure (Finkel & Law, 2011; Finkel & Hays, 2013). Produced and flowback water

contain candidate endocrine disruptors, so there is a very relevant concern about the

disposal of this wastewater (Kassotis et al., 2013). It has been stated that more than 750

chemicals are used during the fracturing process, and of these 750 chemicals more than

100 are known or suspected endocrine-disrupting chemicals (Kassotis et al., 2013).

Another study has published that of an identified 1021 hydraulic fracturing chemicals 781

lacked reproductive and developmental toxicity information (Elliot et al., 2016). 240 of

these chemicals had information available for comparison, and 126 had information on

reproductive toxicity. Of these 126 chemicals with reproductive toxicity data 103 were

possibly associated with adverse reproductive effects (Elliot et al., 2016). The issue of groundwater contamination resulting from hydraulic fracturing is a concern in most communities where the industry is located. New York has on record that the fracturing fluids contain formaldehyde, acids and many other harmful chemicals (Kargbo et al.,

2010). A study on water well quality in Pavillion, WY, reported that natural gas drilling related chemicals were present in several wells tested (Kargbo et al., 2010). A later study by the USGS stated that the Pavillion WY contamination could not related to fracturing operations (Vidic et al., 2013). Contamination has been reported in the tributaries of the

Ohio River within Pennsylvania, due to wastewater treatment facilities not being able to handle the waste present in the produced water; this led to the formation of brominated hydrocarbons in drinking water supplies (Howarth et al., 2011). Wastewater injection 20 wells in Texas and West Virginia have been under close observation because of the

potential for groundwater contamination (Kargbo et al., 2010).

Radium is also a topic of concern when talking about environmental and health

effects of produced/ flowback wasters. Ra226 a known cancer causing substance, occurs in these wastewater steams as naturally occurring radioactive material (NORM). With the potential to have a concentration present in this wastewater of 9,280 pCi/L roughly 1,856 times greater than the drinking water standard of 5 pCi/L. There is a cause for concern when handling the disposal of these wastewaters (U.S. EPA, 2009; Barbot et al., 2013).

2.3 Naturally Occurring Radioactive material (NORM)

Produced waters also contain NORM. Ra226 and Ra228 are the decay products of

U238 and Th232. The presence of Ra226 and Ra228 in the composition of produced water is

another area of concern because in subsurface environments radium can be soluble and

become mobile in groundwater. Radium can become an environmental hazard because it

can bio accumulate in plants and animals, causing health issues such as increased risk of

cancer (Rowan et al. 2011; U.S. EPA, 2009).

NORM has similar characteristics to produced water in the way that over time

NORM concentrations increase over time of production, this was seen in a Green County

Pennsylvania study (Rowan et al., 2011). The disposal of NORM in produced waters

becomes a major point of interest because the drinking water standard for Ra226 is 5

pCi/L, and produced waters have been recorded at levels reaching 9,280 pCi/L (U.S.

EPA, 2009; Barbot et al., 2013). Detection of the amount of radium present in produced

water can be difficult because the presence of so many constituents within the produced

water can cause false negatives when being tested (Viel et al., 2004). Radium is a 21 particular point of concern when working with produced water treatment because it has the tendency to co-precipitate with barium and strontium, which are both very prevalent in produced waters and are treated for removal (Kirby & Salutsky, 1964). It is important to understand this so that precautions can be taken, and treatment steps can be arranged in a way that minimizes radioactive waste. NORM is just one of the many constituents in produced water that make it difficult to treat or dispose of.

2.4 Treatment and Disposal Methods

There are three main methods of fracking wastewater treatment and disposal being used: deep well injection, treatment at private industrial wastewater facilities, and treatment at a municipal wastewater treatment facilities. Deep well injection accounts for over 95% of natural gas wastewater disposal (Lutz et al., 2013). Deep well injection is the most common form of produced water disposal because it is a very low cost disposal method, injection only costs about $0.40- $1.75 per barrel (Mondal & Wickramasinghe,

2008). The problem with this strategy is that injection wells are not always close to the drilling sites, increasing the cost of disposal depending on how far the wastewater needs to be transported. Trucking to dispose of produced water can add roughly $2.00-$4.00 per barrel (Rassenfoss, 2011; Tirreno, 2014). Class II disposal wells are the wells that are allowed to accept brines associated with oil and gas production, and hydrocarbons for storage (ODNR, 2015). Pennsylvania only has 5 operating Class II disposal wells, West

Virginia has 63 operating disposal wells, while Ohio has 210 (Vidic et al., 2013; ODNR,

2015). This disposal method has caused and been associated with groundwater contamination. Between 1982 and 1984 Texas reported 100 confirmed cases of groundwater contamination from injection wells (Vidic et al., 2013). Deep well injection 22 has also been associated with seismic activity and causing earthquakes in areas where

deep well injection wells are located. Earthquakes that occurred in Youngstown, Ohio, in

2011 and central Oklahoma in 2011 appear to have been induced by wastewater injection

wells (Ellsworth, 2013).

Municipal wastewater treatment facilities have been used to treat fracking

wastewater water but have had some major issues when trying to treat the water. These

municipal wastewater facilities were simply not designed to handle the amount of

barium, strontium, and possible radioactive wastes in the water (Howarth et al., 2011).

These facilities also struggle with handling the high TDS loads. In mid-April 2011, The

Pennsylvania Department of Environmental Protection issued a notice stopping the

treatment of fracking wastewater in 15 public water treatment facilities (Rassenfoss,

2011). Policy such as this made industries start to research and use treatment systems that

would allow them to reuse produced water or meet criteria to dispose of it into

watersheds, and at the same time prove to be a valid economic treatment source.

Research has gone into treatment options such as demineralization systems, thermal evaporation/ condensation, and reverse osmosis. These treatment systems all have associated operational issues. Demineralization systems involve pretreatment filtration, thermal evaporation/ condensation systems have limitations of TDS around

150,000 mg/L, and reverse osmosis systems have trouble operating at full efficiency for more than 30 days (Gaudlip et al., 2008). Table 2 compares the cost of a variety of

treatment/disposal options. As can be seen from Table 2 surface disposal and deep well

injection are among two of the cheapest disposal methods, and treatments such as reverse osmosis are among the more expensive options. 23 Table 2: The cost of treating 1000gal of hydraulic fracturing flowback/ produced water with various treatment strategies (Ziemkiewicz et al., 2012). Treatment Method Cost/1000gal

Surface Disposal $0.07

Deep Well Injection-existing $0.66

Spray Irrigation $1.08

Microfiltration $1.36

Electro-coagulation $2.00

Evaporative pond/infiltration $2.98

Water hauling $4.82

Nano filtration $6.15

Reverse Osmosis $6.94

Evaporative Pond-lined $27.56

Beyond these treatment/ disposal strategies acid mine drainage has gained

attention as a possible treatment because of its ability to precipitate Ba+2, Sr+2, and Ra+2

as sulfates (Kondash et al., 2014). While it is not yet a viable treatment method this study explores its potential as a produced water treatment strategy. 24 2.5 Precipitation Treatment

Heavy metals can be removed from solutions through precipitation reactions.

These reactions rely on the exchange of cations and anions, through ion exchange

reactions. These reactions have been used to treat acid mine drainage, and the same

treatment can be used to precipitate heavy metals from produced waters (Feng et al.,

2000). Ion exchange reactions are dependent upon many factors including ionic content,

supersaturation degree, solubility rules, pH, and the content of the produced water (Feng

et al., 2000; Li, 2011). The factors listed above can influence the removal of targeted

constituents from solution. A study published by The University of Pittsburgh noted that

using acid mine drainage to precipitate barium and strontium that a pH of 6.1 removed

barium effectively but not strontium (Li, 2011). Occurrences such as the formation of

acids during precipitation treatments may also need to be accounted for during

treatments. The formation of acids can keep the pH of the solution low inhibiting the

removal of targeted constituents. Hydrogen compensation is often done to buffer the

formation of these acids allowing the reaction to fully take place. Precipitation reactions

target specific constituents, but other constituents present in the solution can co-

precipitate (Tchobanoglous, 2003). Depending upon solution composition these co-

precipitants may be helpful or harmful. Strontium sulfate co-precipitating with barium sulfate may be helpful, but radium sulfate co-precipitating could be problematic (Rowan et al., 2011; U.S. EPA, 2009).

2.6 Acid Mine Drainage as an Alternative Sulfation Feedstock

With water resources becoming scarcer over time, other sources of freshwater will have to be exploited. One potential area that could prove to be a valuable water source to 25 the fracking industry is acid mine drainage (AMD). AMDs major cause is accelerated

oxidation of iron pyrite and other sulphidic minerals resulting from the exposure of these

minerals to both oxygen and water. During the formation of AMD, sulfuric acid is

produced and is present within the mine water. The sulfuric acid is formed through the

interaction of water and air with sulfide compounds in coal or adjacent rocks. The

discharging mine water has concentrations of sulfuric acid (H2SO4), that range from 100-

50,000 ppm H2SO4 (Hoffert, 1947). In the Utica and Marcellus Shale region there is an

abundance of AMD discharge sites from past coal mining operations. This AMD has the potential to be used to treat produced water because of the presence of sulfate in its composition. The treatment strategy currently used by Ohio University uses sulfuric acid to precipitate barium and strontium from produced waters in the sulfation stage of the precipitation process. The sulfuric acid or sulfate in AMD discharge has the potential to do the same treatment while also providing another water source to be used by the industry. AMD has proven to be useful in treating fracking wastewater for radium as well. A study done by Duke University reported that they saw 70-90% radium removal when low pH (3.4) AMD was used, and 50-80% removal rates when a high pH (10-11)

AMD was used (Kondash et al., 2014). Aside from the removal of radium the study also reported that the fracking wastewater used in the experiment also showed decreased amounts of barium and strontium. Kondash et al. (2014) used mixtures of 25, 50, and

75% AMD to fracking wastewater in total volumes of 50 mL. This study will used the data from the precipitation batch experiments to mix a specific amount of AMD water to fracking wastewater to remove a targeted amount of barium. By using specific amounts of AMD a cleaner more efficient treatment can be achieved rather than the percent ratios 26 used by Kondash et al. (2014). AMD has been used in hydraulic fracturing operations previously when 3 million gallons were obtained from the Blue Valley Fish Culture station and used to complete a fracturing operation (Kargbo et al., 2010). The use of

AMD as a fracking wastewater treatment strategy has the potential to reduce the use of freshwater for fracturing operations, using an already contaminated water source for treatment, and decreases the amount of salts and other constituents that would need to be removed from the wastewater (Kondash et al., 2014).

27 CHAPTER 3: METHODS

3.1 Stock Solution Composition

For the equilibrium studies on precipitation of Ba+2, Sr+2, Mg+2, and Ca+2 four synthetic stock solutions were made. The concentrations of the solutions used in this study are listed in Table 3, Table 4 lists the amounts of chemical used to achieve the appropriate concentrations. These four solutions are labeled as High IC (4), High IC (2),

Medium IC (1), and Low IC (0.5). The numbers following the solution names represent ionic strength of the solution. These solutions represent produced water composition. The solution compositions are based upon produced water compositions from northeast

Pennsylvania (Barbot et al., 2013). The solutions were mixed on a stir plate at 350 rpm at

80° C for 15 min once all necessary chemicals were added to the solution and the solution was diluted to the desired mark with deionized water. 15 mL of the stock solution was then filtered with a 0.45 µm syringe tip filter and diluted at a dilution factor of 1000 for analysis on ICP. ICP is the instrument used to determine the concentration of the cations in solution. ICP or Inductively Coupled Plasma uses argon plasma as aerosol to disassociate molecules and then they are filtered and read by a mass spectrometer

(Elmer, 2001). ICP can be used to measure multiple ions making it very ideal for mass analysis, combined with the instruments potential to detect levels at or below 1ppt it is ideal for trace metal analysis (Elmer, 2001). This was done to determine the initial concentrations within the stock solution, specifically barium, magnesium, and calcium because they are key elements when calculating dosing amounts.

28 Table 3: Stock solution target cation/ anion concentrations + 2+ 2+ 2+ 2+ 2+ 2+ - - Na Ca Ba Mg Sr Fe Mn HCO3 Cl Solution Name (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) High IC (4) 64,000 27,500 5,000 2,000 2,500 50 5 6,000 182,454 High IC (2) 35,000 14,000 2,500 1,000 1,250 25 2.5 6,000 97,422 Medium IC (1) 16,000 6,500 1,500 650 1,000 10 1 3,000 45,838 Low IC (0.5) 8,300 3,300 750 350 500 5 0.5 1,000 23,246

The amount of chemical used to reach the concentrations needed to make 1000 ml of solution listed above are shown in Table 3.

Table 4: States the amount of chemical in grams that should be weighted and added to each of the stock solutions. Solution NaCl2 CaCl2 BaCl2 • MgCl2 SrCl2 • FeCl2• MnCl2 NaHCO3 Name (g) (g) 2H2O (g) 6H2O 4H2O (g) (g) (g) (g) (g) High IC 162.686 76.1489 8.8932 7.8342 7.6072 0.1780 0.0115 8.2606 (4) High IC 88.9691 38.7667 4.4466 3.9171 3.8036 0.0890 0.0057 8.2606 (2) Med IC 40.6716 17.9988 2.6680 2.5461 3.0429 0.0356 0.0023 4.1303 (1) Low IC 21.0984 9.1379 1.3340 1.3710 1.5214 0.0178 0.0011 1.3768 (0.5)

3.2 Equilibrium Studies

Objective 1 will be answered through equilibrium studies.

3.2.1 Sulfation

Sulfation, Equation 1, the first stage of the precipitation treatment process used

sulfuric acid (H2SO4) to target the removal of barium from the four synthesized stock solutions. While barium sulfate (BaSO4) is the desired precipitant, radium sulfate

(RaSO4), strontium sulfate (SrSO4), and gypsum (CaSO4 ·2H2O) may also form

(Tchobanoglous, 2003). 29 BaCl2 (aq) + H2SO4 (aq) ↔BaSO4(s) + 2HCl (aq). (1)

ICP, 50 mL, and 15 mL tubes were labeled appropriately for the number of samples that were run in the trial. The 50 mL tubes were then packed with stock solution using a volumetric flask and pipette to achieve an accurate measurement. The samples were then dosed with 18M sulfuric acid (under the fume hood) with amounts predetermined according to a dosing matrix shown in Figure 1. Each dose was performed in triplicate. After dosing with sulfuric acid the samples were placed on the shaker plate for 30 min at 250 rpm. The samples were removed from the shaker plate carefully to avoid disturbing the pellets. Using a syringe and 0.45 µm syringe tip filter, 15 mL of the samples was filtered and placed into the already prepared 15 mL centrifuge tubes. The samples were then ready for dilution for ICP. The samples were diluted by a factor of

1000 and placed in the prepared ICP tubes. After analysis on the ICP, data analysis was done to determine the percent removal rates of Ba2+, Ca2+, Sr2+, Mg2+, Fe2+, Na+, and

Mn2+ for each sample, and the average removal rate of each triplicate as well as standard deviation of each triplicate. This data was then used to determine the next step of optimizing the amount of sulfuric acid used. The goal was to find the smallest amount of sulfuric acid necessary to remove 90% of barium from the stock solution. Strontium is also removed during this stage of treatment as strontium sulfate, which is why no specific treatment is used for its removal. Once a sequence had been optimized it was tested on the other stock solutions to prove efficiency. Initial dosing rates between 0.1 and 100mM were used based on the molar ratio of sulfate to barium (Figure 1).

Figure 1. Flow chart followed for sulfation testing.

3.2.3 Hydrolysis

Hydrolysis, Equation 2, the second or third stage of the precipitation treatment process used sodium hydroxide (NaOH) to target the removal of magnesium from the four synthesized stock solutions. While magnesium hydroxide is the targeted precipitant

sodium hydroxide (NaOH), barium hydroxide (Ba(OH)2), strontium hydroxide (Sr(OH)2)

and calcium hydroxide (Ca(OH)2) may also form (Tchobanoglous, 2003).

MgCl2 (aq) + 2NaOH(aq) --> Mg(OH)2(s) + 2NaCl(s) (2) 31 ICP, 50 mL, and 15 mL tubes were labeled appropriately for the number of

samples that were run in the trial. The 50 mL tubes were then packed with stock solution

using a volumetric flask and pipette to achieve an accurate measurement. The samples

were then dosed with 10M sodium hydroxide using a dosing matrix based on the molar

ratio of hydroxide to magnesium between 0.6 and 1.4 (Figure 2). If this step was done

second in the treatment process hydrogen compensation was used to account for the

formation of hydrochloric acid in the sulfation treatment, Equation 3. Sulfation

precipitates BaSO4, it also forms hydrochloric acid (HCl). The formation of this acid

needed to be accounted for in the second step of the treatment to ensure the reaction fully

took place and removal was achieved. The presence of this acid could keep the pH low

inhibiting the reaction. To account for the HCl in solution if hydrolysis was done as the

second treatment more NaOH was used during treatment than is necessary for just

removal of magnesium. The overtreatment of NaOH buffers the HCl in solution and achieves the targeted removal of magnesium. (Tchobanoglous, 2003).

BaCl2 (aq) + H2SO4 (aq) ↔BaSO4(s) + 2HCl (aq) (3)

Each dose was performed in triplicate. After dosing with 10M sodium hydroxide, the samples were placed on the shaker plate for 30 min at 250 rpm. The samples were then removed from the shaker plate carefully to avoid disturbing the pellets. Using a syringe and 0.45 µm syringe tip filter, 15 mL of the samples was filtered and placed into the already prepared 15 mL centrifuge tubes. The samples were now ready for dilution for ICP. The samples were diluted by a factor of 1000 and placed in the prepared ICP tubes. After analysis on the ICP, data analysis was done to determine the percent removal rates of Ba2+, Ca2+, Sr2+, Mg2+, Fe2+, Na+, and Mn2+, for each sample, the average 32 removal rates of each triplicate as well as standard deviation of each triplicate was also performed. The goal was to find the least amount of sodium hydroxide necessary to remove 90% of magnesium from the stock solution. Once a sequence had been optimized it was tested on the other stock solutions.

Start with one solution from Section III.A

Use ratio between Did 0.8 0.6 and 0.8 to OH : Mg Yes result in >90% result in removal until 90% >90% Fe removal efficiency removal? is achieved. Record dose.

Use ratio between Did 1.0 0.8 and 1 to result OH : Mg Yes in >90% removal result in until 90% removal >90% Fe efficiency is removal? achieved. Record Once optimal dose dose. Proceed to is determined softening after the proceed to the No optimal dose for next solution until each solution is all solutions are determined. Use ratio between complete. Did 1.2 1 and 1.2 to result OH : Mg Yes in >90% removal result in until 90% removal >90% Fe efficiency is removal? achieved. Record dose.

Use ratio between Did 1.4 1.2 and 1.4 to OH : Mg Yes result in >90% result in removal until 90% >90% Fe removal efficiency removal? is achieved. Record dose.

Re-evaluate doses and experimental variables preventing removal before proceeding.

Figure 2. Flow chart followed for hydrolysis testing.

33 3.2.3 Softening

Softening, Equation 4, the second or third stage of the precipitation treatment

process uses sodium carbonate (NaCO3) to target the removal of calcium from the four

synthesized stock solutions. While calcium carbonate (CaCO3) is the desired precipitant,

sodium carbonate (Na2CO3), barium carbonate (BaCO3), strontium carbonate (SrCO3)

and magnesium carbonate (MgCO3) may also form (Tchobanoglous, 2003).

CaCl2 (aq) + 2NaCO3 (aq) --> 2NaCl (aq) + Ca(CO3)2 (aq) (4)

ICP, 50 mL, and 15 ml tubes were labeled appropriately for the number of

samples that were run in the trial. The 50 mL tubes were then packed with stock solution

using a volumetric flask and pipette to achieve an accurate measurement. The samples

were then dosed with 2M sodium carbonate using a dosing matrix based on the molar

ratio of carbonate to calcium between 0.6 and 1.4 (Figure 3). If this step was done second

in the treatment process hydrogen compensation was used to account for the formation of

hydrochloric acid in the sulfation treatment, Equation 3. Sulfation precipitates BaSO4, it

also forms hydrochloric acid (HCl). The formation of HCl needed to be accounted for in

the second step of the treatment to ensure the reaction fully took place and removal was

achieved. The presence of this acid could keep the pH of the solution low inhibiting the

reaction. To account for the HCl in solution, if softening was done as the second

treatment then more Na2CO3 was used during treatment than was necessary for removal

of magnesium. The overtreatment of Na2CO3 buffers the HCl in solution and achieves the targeted removal of magnesium. (Tchobanoglous, 2003).

Each dose was performed in triplicate. After dosing with sodium carbonate, the samples were placed on the shaker plate for 30 min at 250 rpm. The samples were then 34 removed from the shaker plate carefully to avoid disturbing the pellets. Using a syringe and 0.45 µm syringe tip filter, 15 mL of the samples was filtered and placed into the already prepared 15 mL centrifuge tubes. The samples were ready for dilution for ICP.

The samples were diluted by a factor of 1000 and placed in the prepared ICP tubes. After analysis on the ICP, data analysis was done to determine the percent removal rates of

Ba2+, Ca2+, Sr2+, Mg2+, Fe2+, Na+, and Mn2+ for each sample, the average removal rates of each triplicate, as well as standard deviation of each triplicate were also calculated. The goal was to find the least amount of sodium carbonate necessary to remove 90% of calcium from the stock solution. Strontium is also removed during this stage of treatment as strontium carbonate which is why no specific treatment is used for its removal. Once a sequence had been optimized it could be tested on the other stock solutions. 35

Figure 3. Flow chart followed for softening testing.

3.3 Kinetics

Objective 2 will be met in this section. The kinetics testing of the precipitation reactions began with the sulfation reaction, Equation 1.

To test the time it takes for this reaction to take place, a filtration method was used. 40 mL of stock solution was placed into a 50 mL centrifuge tube. 1.5 µm filters

(same size used in equilibrium studies experiments) were then placed in the oven for 15 min at 105°C to dry, then their weight was recorded. Based on the batch experiments, the 36 stock solution was dosed at a 1.1 molar ratio of sulfate to barium for sulfation, a 0.8 ratio

of hydroxide to magnesium for hydrolysis, and a 0.9 ratio of carbonate to calcium, for

softening. The solutions were dosed under the fume hood and placed on the vortex mixer

for the remainder of the reaction time. When the appropriate reaction time was achieved,

the solution was quickly vacuum filtered, and the filter was placed in the oven to dry for

at least two hours at 105°C. After drying, the mass of the filter was recorded and data

analysis was done to determine the amount of precipitate present on the filter. Based on

the scoping trials for each treatment optimization reaction times were determined. This

process was repeated for the reactions of softening, and hydrolysis, equations 2 and 4.

These tests were conducted in two stages. The first stage of the experiment was a

scoping test to see when the reaction occurs. This scoping test was done with one sample

from each reaction time. The scoping reaction times were 1800, 600, 300, 180, 120 and

60 seconds. After the reaction time was optimized, a second test was done with triplicate samples at the reaction times. The optimization reaction times that were tested were 600,

120, 60, 40, and 20 seconds for sulfation and 600, 90, and 45 seconds reaction times were used for hydrolysis and softening. Kinetics testing was done in the following order: sulfation first, hydrolysis as stage two then softening as stage three. Testing also took place as sulfation first softening as stage two and hydrolysis as stage three. Low IC (0.5) stock solution and High IC (4) stock solution were tested in these kinetics tests.

3.4 Acid Mine Drainage Treatment

Objective 3 will be met in this section. Acid mine drainage as a possible substitute

for sulfuric acid in the treatment of produced waters was tested as follows. The site used

for this research was the discharge from the Rice-Hocking AS-14 mine in Carbondale, 37 Ohio; site number HF133 in the Ohio Watershed Data web geodatabase (Ohio Watershed

Data, 2015). This site was selected because of its consistently high sulfate concentration averaging 1068 mg/L, based on thirty samples from 2001-2014, posted in the web-based geodatabase (Ohio Watershed Data, 2015). Upon selection of the acid mine drainage site, a grab sample of water was analyzed to determine the concentration of sulfate present.

The determination of the sulfate content present in the acid mine discharge was determined using the Hach manual, method 8200, on the Hach spectrometer, model

DR2800. The same stock solutions tested in the precipitation stage of the project were used for testing. Testing began with the Low IC (0.5) solution and moved up to the High

IC (4) solution. 50 mL centrifuge tubes were filled with between 5 and 40 mL of stock solution and dosed with AMD following the methodology stated in section 4.2 Sulfation.

The reason for the volume variation was that the higher concentration stock solutions needed more AMD treatment, so the amount of stock used for the experiment was calculated so the experiments could be performed in 50 ml centrifuge tubes. The solution was left to react for 30 min and then run on ICP for data analysis. The test matrix used is shown below (Figure 4).

Figure 4. Flow chart followed for acid mine drainage testing.

39 CHAPTER 4: RESULTS AND DISCUSSION

4.1 Batch Experiments

Objective:

1. To determine amount of dosing agent to remove 90% or alternative

sufficient removal rate of Ba+2, Sr+2, Ca+2 and Mg+2.

Deliverable: Provide data with conclusive evidence that 90% or alternative

sufficient removal rate of Ba+2, Sr+2, Ca+2, and Mg+2 can be achieved.

Batch experiments were conducted in two treatment orders, sulfation- hydrolysis- softening, and sulfation- softening- hydrolysis. These treatment orders were conducted on four synthetic stock solutions Low IC (0.5), Medium IC (1), High IC (2), and High IC

(4). During this discussion it is important to note that that numbers in front of the treatments (1.1 sulfation), represent the molar ratio of dosing agent to targeted cation. In this case the treatment is 1.1 moles of sulfate to every mole of barium. This is applied to hydrolysis, NaOH: MgCl2, and softening NaCO3: CaCl2. Complete data on batch experiments testing are shown in Appendix 1

Figures 5a and 5b represent the results from Low IC (0.5). As shown in Figure 5a,

1.1 sulfation dose resulted in a 99% removal of barium from solution. A 0.9 softening dose that resulted in a 93-94% removal of calcium from solution. Hydrolysis was dosed at four treatments 0.8, 1, 1.2, 1.4. At the 0.8 treatment there is a removal of 94%, at the 1,

1.2, 1.4 treatments 100% of magnesium was removed from solution. The removal of magnesium increased with an increased treatment dose. Strontium removals varied from

73-78% and did not increase with the increase in hydrolysis treatment. 40 In Figure 5b, a 1.1 sulfation dose resulted in a 99-100% removal of barium from solution. A 0.8 hydrolysis treatment resulted in a removal of 93-98% of magnesium from solution. Magnesium removals increased with the increased softening treatments. At 0.8

93% of magnesium was removed from solution, at 1 95%, 1.2 97%, and 1.4 98%. This is due to magnesium co-precipitating as MgCO3 from solution. Softening was dosed at four treatments 0.8, 1, 1.2, 1.4. At 0.8 89% removal of calcium was observed, at treatment 1

89% removal, at treatment 1.2 100%, and at treatment 1.4 100% removal. Strontium removal was between 79-100%, removal increased with the increasing softening treatments. Strontium removal was 79% at 0.8, 89% at 1, 100% at 1.2, and 100% at 1.4.

This occurrence is due to the co-precipitation of strontium as strontium carbonate

(SrCO3).

Figure 5a and 5b. Low IC (0.5) removal results with hydrolysis stage 3 and softening stage 3. Treatments based on the molar ratio of dosing agent to targeted cation, sulfuric acid to barium, sodium carbonate to calcium, sodium hydroxide to magnesium. Strontium was not specifically treated for, but removal occurred through co-precipitation during the sulfation, softening, and hydrolysis treatments.

42 Figures 6a and 6b represent the results from Medium IC (1). In Figure 6a, a 1.1

sulfation dose resulted in a 99% removal of barium from solution. A 0.9 softening dose

resulted in an 84-85% removal of calcium from solution. Hydrolysis was dosed at four

treatments 0.8, 1, 1.2, and 1.4. At 0.8 86% of magnesium was removed from solution, at

1, 1.2, and 1.4 100% removal was observed. The removal of magnesium increased with

an increase in treatment from 86% at 0.8 treatment to 100% at treatment 1. Strontium

removals were consistent at 56%.

In Figure 6b, a 1.1 sulfation dose resulted in a 99-100% removal of barium from

solution. A 0.8 hydrolysis treatment resulted in a 99-100% removal of magnesium from

solution. Softening was dosed at four treatments 0.8, 1, 1.2, and 1.4. At 0.8 77% of

calcium was removed from solution, at treatment 1 94%, at treatment 1.2 100% and at

treatment 1.4 100%. Strontium removal varied from 50-100%, it increased with the

increased softening treatments. At treatment 0.8 50% strontium removal was observed, at treatment 1 79%, at treatment 1.2 99% and at treatment 1.4 100%. The increase in strontium removal with the increase in softening treatment is due to strontium co- precipitating as SrCO3 from solution. 43

Figure 6a and 6b. Medium IC (0.5) removal results with hydrolysis stage 3 and softening stage 3. Treatments based on the molar ratio of dosing agent to targeted cation, sulfuric acid to barium, sodium carbonate to calcium, sodium hydroxide to magnesium. Strontium was not specifically treated for, but removal occurred through co-precipitation during the sulfation, softening, and hydrolysis treatments.

44 Figures 7a and 7b represent the results from High IC (2). In Figure 7a 1.1 sulfation dose resulted in a 99% removal of barium from solution. A 0.9 softening dose resulted in an 83-86% removal of calcium from solution. Hydrolysis was dosed at four treatments 0.8, 1, 1.2, and 1.4. At 0.8, 1, 1.2, and 1.4 99% of magnesium was removed from solution. Strontium removal was consistent at 58%.

Figure 7b, 1.1 sulfation dose resulted in a 100% removal of barium from solution.

A 0.8 hydrolysis dose resulted in a 99-100% removal of magnesium from solution.

Softening was dosed at four treatments 0.8, 1, 1.2, and 1.4. At 0.8 88% of calcium was removed from solution and at 1, 1.2, 1.4 100% of calcium was removed from solution.

Strontium removal varied from 70-100%, but increased with the increase in softening treatments. At 0.8 70% of strontium was removed from solution, at treatment 1 99%, at treatment 1.2 100%, and at treatment 1.4 100%. The increase in strontium removal with the increase in softening treatment is due to the strontium co-precipitating as SrCO3.

Figure 7a and 7b. High IC (2) removal results with hydrolysis stage 3 and softening stage 3. Treatments based on the molar ratio of dosing agent to targeted cation, sulfuric acid to barium, sodium carbonate to calcium, sodium hydroxide to magnesium. Strontium was not specifically treated for, but removal occurred through co-precipitation during the sulfation, softening, and hydrolysis treatments.

46 Figures 8a and 8b represent the results from treatment on High IC (4). In Figure

8a a 1.1 sulfation dose results in a 98% removal of barium from solution. A 0.9 softening dose resulted in an 89% removal of calcium from solution. Hydrolysis was dosed in four treatments 0.6, 0.7, 0.8, and 1. At 0.6 61% of magnesium was removed from solution, at treatment 0.7 63%, and treatment 0.8 65% and at treatment 1 69%. Strontium removals were between 56-57% removals from solution.

In Figure 8b a 1.1 sulfation dose resulted in a 97-98% removal of barium from solution. A 0.8 hydrolysis treatment resulted in a 100% removal of magnesium from solution. Softening was dosed at four treatments 0.6, 0.7, 0.8, and 1. At 0.6 55% of calcium was removed from solution, at treatment 0.7 61%, at treatment 0.8 70% and at treatment 1 84%. Strontium removals were between 41-64%, but increased with the increasing softening treatments. At 0.6 41% of strontium was removed from solution, at treatment 0.7 47%, at treatment 0.8 55% and at treatment 1 64%. This increase in strontium removal with the increase in softening treatment is due to the co-precipitation of strontium as SrCO3. 47

Figure 8a and 8b. High IC (4) removal results with hydrolysis stage 3 and softening stage 3. Treatments based on the molar ratio of dosing agent to targeted cation, sulfuric acid to barium, sodium carbonate to calcium, sodium hydroxide to magnesium. Strontium was not specifically treated for, but removal occurred through co-precipitation during the sulfation, softening, and hydrolysis treatments. 48 The treatment order makes a difference in the removal of the targeted cations, when softening is done as stage 3 treatment there are increased removals of strontium and calcium from solution. There is not as much removal of strontium or calcium from solution when hydrolysis is done as stage 3 treatment. This is likely due to the difference in pH at these treatments. Table 5 shows when softening is done as stage 2 treatment the pH is 6.3- 7.8, when softening is done as stage 3 treatment the pH is 7.7-10.8. For maximized removal efficiency sulfation at a treatment of 1.1, hydrolysis at treatment 0.8, and softening at treatment 1.2 show the best results for optimal removal of barium, strontium, calcium and magnesium from solution. This conclusion meets the first deliverable of the project. Sodium carbonate is more expensive than sodium hydroxide.

Sodium carbonate is $0.019279/ mol, and sodium hydroxide is $0.017637/ mol (Institute for Sustainable Energy and the Environment, 2015). If calcium removals above 80% are sufficient and strontium is not prevalent in the produced water then hydrolysis at stage 3 treatment would be more cost effective. The treatment order is relative to the composition of the produced water that is being treated depending on what constituents are present and the concertation of those constituents a treatment order can be decided that both satisfies removals and the most cost effective solution. 49 Table 5: Solution pH During Precipitation Treatments

Treatment Low IC (0.5) Medium IC (1) High IC (2) High IC (4) Sulfation - Hydrolysis - Softening pH pH pH pH Sulfation 1.1 6.865 5.852 5.571 Sulfation 1.1 5.002

Hydrolysis 0.8 10.480 10.565 11.163 Hydrolysis 0.8 11.038

Softening 0.8 8.421 7.720 10.732 Softening 0.6 10.838

Softening 1 8.149 7.898 10.765 Softening 0.7 10.805

Softening 1.2 8.578 8.516 10.630 Softening 0.8 10.744

Softening 1.4 10.145 9.681 10.577 Softening 1 10.364

Sulfation- Softening - Hydrolysis Sulfation 1.1 6.685 5.852 5.571 Sulfation 1.1 5.002

Softening 0.9 7.878 7.355 6.895 Softening 0.9 6.306

Hydrolysis 0.8 11.378 10.141 9.372 Hydrolysis 0.6 9.218

Hydrolysis 1 11.685 11.105 9.551 Hydrolysis 0.7 9.486

Hydrolysis 1.2 11.511 10.952 9.536 Hydrolysis 0.8 9.087

Hydrolysis 1.4 11.789 11.776 9.981 Hydrolysis 1 9.558

4.2 Kinetics

Objective:

2. To determine the reaction time of each equilibrium reaction.

Deliverable: Provide a reaction time that deems that equilibrium reactions

complete. 50 Kinetics testing was done to determine the time it takes for the treatment reactions to take place. Testing was conducted on Low IC (0.5) and High IC (4) for each treatment step and order. Complete data on the kinetics testing are shown in Appendix 2.

Figure 9a and Figure 9b show the results of the scoping and optimization for sulfation stage 1 trials performed on the Low IC (0.5) (Figure 9a) and High IC (4) (Figure

9b) solutions.

Figures 9a and 9b show at the 20 s reaction time there is a decrease in amount of removed barium from solution. This is most likely due to the fact that the reaction is still taking place at this reaction time. After the 60 s reaction time period the removal of barium decreases and there is more separation within the data. Based on this information

60 s would be the optimal reaction time to gain the targeted removal of barium from solution.

Figure 9a-9b. Optimization and scoping results from the Low IC (0.5) and High IC (4) kinetics trials. At the 20 second reaction time period there is a noticeable reduction in removal in both cases. This is most likely due to the reaction still taking place at this reaction time. Legend Located at top of Figure 9a.

52 Figure 10a and Figure 10b show the results of the scoping and optimization for hydrolysis stage 2 trials performed on the Low IC (0.5) (Figure 10a) and High IC (4)

(Figure 10b) solutions. Figure 11a and 11b show the results of the scoping and optimization for hydrolysis stage 3 trials performed on the Low IC (0.5) (Figure 11a), and

High IC (4) (Figure 11b).

Figure 10a shows a consistent removal average of 88% at the 90 s and 45 s reaction times, but when compared to the removal rates in the High IC (4) solution the removal rates are much higher in the High IC (4), Figure 10b. At the 90 s reaction time the removal rate is 114% and at the 45 s reaction time 110%. This can be attributed to the fact that there is co-precipitation at this treatment stage. Magnesium is being removed from solution but other constituents are also precipitation during the reaction. While magnesium hydroxide is the targeted precipitant sodium hydroxide (NaOH), barium hydroxide (Ba(OH)2), strontium hydroxide (Sr(OH)2) and calcium hydroxide (Ca(OH)2) may also form during the ion exchange reactions (Tchobanoglous, 2003). Analysis was not done to determine what exactly was co-precipitating, but the increased removal rates can be attributed to these other likely precipitants. This co-precipitation event was also observed when hydrolysis was performed as treatment stage 3. The Low IC (0.5) showed removal rates of 84% at the 45 s reaction time and 89% at the 90 s reaction time, Figure

11a. The High IC (4) saw removal rates of 100% at the 90 s reaction time and 116% at the 45 s reaction time, Figure 11b. 53

Figure 10a and 10b. Optimization and scoping results from the Low IC (0.5) and High IC (4) hydrolysis stage 2 kinetics trials. The High IC (4) solution shows increased removal rates at the 90 s and 45 s reaction times most likely du e to co-precipitation events, Figure 10b. Legend located at top of Figure 10a. 54

Figure 11a and 11b. Optimization and scoping results from the Low IC (0.5) and High IC (4) hydrolysis stage 3 kinetics trials. The High IC (4) solution shows increased removal rates at the 90 s and 45 s reaction times most likely due to co-precipitation events, Figure 11b. This is a similar trend to the results of hydrolysis treatment as stage 2. Legend located at top of Figure 11a.

Figure 12a and Figure 12b show the results of the scoping and optimization for softening stage 2 trials performed on the Low IC (0.5) ( Figure 12a) and High IC (4) 55 (Figure 12b) solutions. Figure 13a and 13b show the results of the scoping and

optimization for softening stage 3 trials performed on the Low IC (0.5) (Figure 13a), and

High IC (4) (Figure 13b). Softening stage 2 low IC (0.5) showed 96% removals at the 45 and 90 s reaction times, meaning that the majority of the reaction has taken place at this

reaction time. The High IC (4) softening stage 2 results show an increase in percent

removal at the 45 and 90 s reaction times. At the 90 s reaction time there was 109%

removal from solution and at the 45 s reaction time there was 125% removal from

solution. The increase in removal is most likely due to co-precipitation within the

softening reaction. While calcium carbonate (CaCO3) is the desired precipitant, sodium

carbonate (Na2CO3), barium carbonate (BaCO3), strontium carbonate (SrCO3) and

magnesium carbonate (MgCO3) may also form (Tchobanoglous, 2003). The increase in

removal is most likely due to the one of these co-precipitants. The high removal rate is not seen at the 600 s reaction time meaning that the co-precipitates seen at the 90 and 45 s reaction times do not stay precipitated for 600 s. This co-precipitation event only occurs at the 90 and 45 s reaction times. Figures 13a and 13b show the results of the scoping and optimization for softening stage 3 trials performed on Low IC (0.5) (Figure 13a) and

High IC (4) (Figure 13b). Similar results were found in softening stage 3 treatment as

softening stage 2 treatment. The High IC (4) showed an increased in percent removal at

the 90 and 45 s reaction times, Figure 13b. At the 90 s reaction time a removal rate of

131% was recorded and at 45 s a removal rate of 158% was recorded. This increase in

evident percent removal is consistent with softening stage 2 results, except there was

more removal at softening stage 3. The Low IC (0.5) results for softening stage 3 showed

an increase in percent removal also, which is not consistent with the Low IC (0.5) 56 softening stage 2 results. During the softening stage 3 treatment the Low IC (0.5) showed a percent removal rate of 107% at 90 s and 117% at 45 s. Overall there was an increase in percent removal in both Low IC (0.5) and High IC (4) during the softening stage 3 treatment.

Figure 12a and 12b. Optimization and scoping results from the Low IC (0.5) and High IC (4) softening stage 2 kinetics trials. Increased percent removals were recorded at the 45 and 90 s reaction times for High IC (4) most likely due to co-precipitation within the reaction, Figure 12b. Legend located at top of Figure 12a. 58

Figure 13a and 13b. Optimization and scoping results from the Low IC (0.5) and High IC (4) softening stage 3 kinetics trials. High IC (4) shows an increased percent removal at the 90 and 45 s reaction times, Figure 13b. Low IC (0.5) also shows increased removals at the 90 and 45 s reaction times, Figure 13a. This is a different trend than was observed in softening stage 2 results. Legend at top of Figure 13a.

The increase in amount of precipitate during the softening stage 2 and 3 treatments at the 45 s and 90 s reaction times is due to the formation of a calcium 59 carbonate hydrate. It has been found that in the presence of a saturated sodium chloride

solution and small amounts of magnesium ion a range of precipitants can occur (Brooks

et al., 1950; Kitano, 1962). Solutions of calcium, magnesium chloride, and sodium

carbonate can create a hydrated double carbonate of calcium and magnesium. This

precipitate also contains sodium, which can explain the increase in precipitate weight

when the precipitate is dried. The precipitant in this case looked like a gel which is

consistent with the findings of Brooks, et al. (1950). The 600 s reaction time did not show an increase in the amount of precipitant which his most likely due to the increase in stir time this trial received. Temperature and stirring are conditions that can affect the formation of the precipitate (Brooks et al., 1950). This also explains why the increase in precipitant decreases from 45 s to 90 s, because the 90 s reaction time received more time stirring. The increase in amount of precipitate at hydrolysis stage 2 and 3 treatments is

similar to the findings of (Tan et al., 2011). This study showed that precipitating

Mg(OH)2 from a MgCl2 solution can cause emulsions and creaming when pH is not

stable. At the reaction times 90 and 45 s, the pH of the solution is not stable and

“creaming “occurs (Tan et al., 2011). This was a consistent finding with the results presented above, a noticeable gel like state was observed at these reaction times. The creaming is due to a unstable pH of the solution and can cause emulsion to take place

which along with the precipitate Mg(OH)2 removed water also. The water removed is from a saturated salt solution so once dried the salt altered the recorded amounts of precipitate, accounting from the increases seen at the reaction times 45 and 90 s. The 600 s reaction time does not show an elevated level of precipitate because the longer reaction time allows the pH to stabilize and minimize the amount of “creaming” occurring which 60 doesn’t remove as much water from solution during the precipitation reaction. This data meets deliverable two of the project.

4.3 Acid Mine Drainage Treatment

Objective:

3. To determine the effectiveness of AMD as a possible reactant feedstock

for the removal of Ba+2.

Deliverable: Determine if Acid Mine Drainage cane effectively remove

barium specific amount of Ba+2 in solution.

Acid mine drainage (AMD) was used to treat the four synthetic stock solutions in substitution for sulfuric acid in the sulfation treatment. AMD was dosed at six molar ratios of dosing agent to the targeted cation, sulfate: barium. The six treatments were 0.8,

0.9, 1, 1.1, 1.2, and 1.4. Complete data on acid mine drainage treatment testing are shown in Appendix 3.

Figure 14 represents the results from acid mine drainage treatment on Low IC

(0.5). At treatment 0.8 63% of barium was removed from solution, at treatment 0.9 63%, at treatment 1 70%, at treatment 1.1 71%, at treatment 1.2 80%, and at treatment 1.4

84%. Strontium removals were low ranging from 1-4%. At treatment 0.8 2% of strontium was removed from solution, at treatment 0.9 1%, at treatment 1 2%, at treatment 1.1 2%, at treatment 1.2 2%, and at treatment 1.4 4%. 61

Figure 14. Low IC (0.5) removal results with AMD as sulfation treatment. Treatments based on the molar ratio of dosing agent to targeted cation, sulfate to barium.

Figure 15 represents the results from acid mine drainage treatment on Medium IC

(1). At treatment 0.8 71% of barium was removed from solution, at treatment 0.9 77%, at treatment 1 83%, at treatment 1.1 88%, at treatment 1.2 91%, and at treatment 1.4 95%.

Strontium removals were low ranging from 2-14%. At treatment 0.8 2% of strontium was removed from solution, at treatment 0.9 2%, at treatment 1 5%, at treatment 1.1 8%, at treatment 1.2 11%, and at treatment 1.4 14%.

Figure 15. Medium IC (1) removal results with AMD as sulfation treatment. Treatments based on the molar ratio of dosing agent to targeted cation, sulfate to barium.

Figure 16 represents the results from acid mine drainage treatment on High IC (2).

At treatment 0.8 70% of barium was removed from solution, at treatment 0.9 76%, at treatment 1 83%, at treatment 1.1 88%, at treatment 1.2 91%, and at treatment 1.4 94%.

Strontium removals were low ranging from 8-16%. At treatment 0.8 8% of strontium was removed from solution, at treatment 0.9 8%, at treatment 1 10%, at treatment 1.1 12%, at treatment 1.2 14%, and at treatment 1.4 16%.

Figure 16. High IC (2) removal results with AMD as sulfation treatment. Treatments based on the molar ratio of dosing agent to targeted cation, sulfate to barium.

Figure 17 represents the results from acid mine drainage treatment on High IC (4).

At treatment 0.8 74% of barium was removed from solution, at treatment 0.9 82%, at

treatment 1 90%, at treatment 1.1 95%, at treatment 1.2 98%, and at treatment 1.4 99%.

Strontium removals were low ranging from 1-4%. At treatment 0.8 0% of strontium was removed from solution, at treatment 0.9 0%, at treatment 1 0%, at treatment 1.1 1%, at treatment 1.2 3%, and at treatment 1.4 4%.

Figure 17. High IC (4) removal results with AMD as sulfation treatment. Treatments based on the molar ratio of dosing agent to targeted cation, sulfate to barium.

The results of acid mine drainage treatment show a trend of high removals of barium, but low removals of strontium. This comes as no surprise for a variety of reasons.

The first is that we were treating specifically for the removal of barium based on a molar ratio of sulfate to barium, strontium was not included in the treatment design. The solubility of strontium sulfate is three orders of magnitude higher than barium sulfate (Li,

2011). The pH values can also have an impact on the removal of strontium from solution as strontium sulfate. In the study done by Li Meng at the University of Pittsburgh a pH of

6.1, barium was still removed efficiently from the solution while strontium did not precipitate nearly as efficiently (Li, 2011). Table 6 shows that the pH of the AMD- synthetic stock solution mixture for our experiments are between 5.8 and 6.5 for all for stock solutions and treatments, the low removal is not surprising based on this 65 information. Figure 18 shows that strontium solubility decreases near a pH of 7, also supporting why low levels of strontium are removed from solution.

Table 6: Solution pH During AMD Treatments Low IC (0.5) Medium IC (1) High IC (2) High IC (4) Treatment pH pH pH pH 0.8 6.328 6.320 6.278 6.233

0.9 6.164 6.505 6.263 6.174

1 6.081 6.269 6.203 6.157

1.1 6.037 6.185 6.162 6.152

1.2 6.008 6.167 6.095 6.122

1.4 5.885 6.150 6.083 6.099 66

Figure 18. Strontium vs. pH, strontium shows solution concentration vs. pH. Strontium solubility is reduced at a pH of 7 leading to precipitation (Owusu, G., & Litz, 2000).

The results obtained are also comparable to Kondash, et al. (2014). This study mixed ratios of 25, 50, and 75% AMD to hydraulic fracturing flowback fluid. They noted low removals of strontium when a low pH (3.4) acid mine drainage was mixed with hydraulic fracturing flowback fluid. The study also showed that the removals of strontium and barium increased with increased ratios of AMD meaning that more sulfate in solution precipitated more strontium. These findings are consistent with the results found in figures 14, 15, 16, and 17, showing an increased amount of strontium removal at increased treatments. 67 This treatment was effective at removing barium from solution, but solution volumes increased over the four stock solutions in regard to amount of stock: AMD. To treat Low IC (0.5) at 1.1 sulfation 12.78 ml of AMD was used to treat 25 ml of stock solution, to treat Medium IC (1) at 1.1 sulfation 10.59 ml of AMD was used to treat 10 ml of stock solution, to treat High IC (2) at 1.1 sulfation 17.35 ml of AMD was used to treat 10 ml of stock solution, and to treat High IC (4) at 1.1 sulfation 18.20 ml of AMD was used to treat 5 ml of stock solution. This data meets deliverable three of the project.

These proportions of AMD to stock solution would cause error due to dilution when calculating the amount of barium removed. The removal rates of barium were calculated based on the mass of barium before and after treatment to avoid error due to dilution. To use AMD treatment to remove barium from produced water the concentration of the produced water and the sulfate concentration of the AMD will play a major role in the size of tank used to for treatment.

68 CHAPTER 5: CONCLUSIONS

5.1 Batch Experiments

Objective 1 and deliverable 1.The sequence of the treatment makes a difference in the removal of the targeted ions barium, strontium, calcium and magnesium from solution. The most efficient treatment sequence is sulfation at treatment 1.1, hydrolysis at treatment 0.8, and softening at treatment 1.2. While this removal sequence shows to be the most efficient for removal of these ions and meets deliverable one of the project, the concentration of the produced water being treated, and the goals of the treatment play a significant role in treatment order. The cost of sodium hydroxide and sodium carbonate

will also influence the treatment order and dosing amounts. Furthermore the

concentrations which are deemed acceptable for reuse or release into a water body will

also influence the treatment order and dosing rates. All of these circumstances can impact

how the solution is treated, but the sequence of sulfation at treatment 1.1, hydrolysis at

treatment 0.8, and softening at treatment 1.2, shows to be the optimal treatment for

maximized removal of the targeted ions barium, strontium, calcium, and magnesium.

Hydraulic fracturing produced water can be treated for the removal of barium,

strontium, calcium and magnesium. This work done in this study is unique because it

allows for treatment at whatever amount of constituent needs to be removed from

solution depending on the intent of the water. Barium, strontium, calcium, and

magnesium can be removed 100% from solution and at any lower percentage. While

100% removal may not be a viable treatment for the present economics of produced

water treatment, this research is viable when the time comes that 100% removal is a

viable economic option. 69 5.2 Kinetics

Objective 2 and deliverable 2.The optimal reaction time for treatment is 60 s for all of the treatments, deliverable two. While it is assumed that these reactions happen instantaneously, based on the experimental method used 60 s is the reaction time the supports a removal between 84- 100% of targeted cations. During the precipitation process hydrates and “creaming” can occur which can cause an increase in precipitate

weight. This phenomenon occurred at hydrolysis stage 2 and 3 treatments, and softening

stage 2 and 3 treatments.

The kinetics testing provided data that showed that the optimal time for the

precipitation reactions to occur is 60 s. This is important information moving forward

with a mobile treatment system because the data will influence the residence time of the

produced water and the tank sized used for treatment. Taking into account the formation

of hydrates during the softening and hydrolysis treatments a method that has good

mixture will also be necessary to avoid major backup during the treatment process.

5.3 Acid Mine Drainage Treatment

Objective 3 and deliverable 3. Acid mine drainage showed to be a viable

treatment for the removal of barium from solution. Based on the sulfate concentration of

a particular source of AMD and the results of the batch experiments, an exact dose can be

calculated for treatment, making the treatment very efficient, deliverable three. Low

removal of strontium was recorded, likely due to the low pH present in solution.

Acid mine drainage proved to be viable treatment for the removal of barium from

the produced water solutions. The potential is there for AMD to be used as a reactant

feedstock to treat produced water solutions. The proportion of AMD that needs to be used 70 to treat produced water will have to be taken in account if this option is used at an industrial scale. A very large tank would need to be used to treat enough water at one time make the process efficient. This work did provide a system that can be applied to efficiently dose produced water with AMD. The information provided in the study allows for the determination of the exact amount of AMD necessary to treat produced water for the removal of barium, making the process more efficient. Economically AMD treatment may not be viable it is option that could be used in the future to treat hydraulic fracturing produced waters.

The results presented in this document provide a treatment for produced waters to remove Ba+2, Sr+2, Ca+2 and Mg+2 through conventional precipitation treatment and alternative AMD treatment. These treatments are a viable option and can contribute to the treatment of hydraulic fracturing produced waters now and in the future.

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76 APPENDIX 1 – BATCH EXPERIMENT RESULTS AND SUMMARY STATISTICS

Appendix 1.1 Low IC (0.5) Results with Hydrolysis as Stage 3 Treatment Hydrolysis Ba AVE SD Ca AVE SD Mg AVE SD Sr AVE SD 99% 94% 95% 78% 0.8 99% 99% 0% 94% 94% 0% 94% 94% 0% 78% 78% 0% 99% 94% 94% 78% 99% 94% 100% 78% Low 1.1 1 99% 99% 0% 94% 93% 1% 100% 100% 0% 77% 75% 5% Sulfation 99% 91% 100% 69% 0.9 99% 94% 100% 78% Softening 1.2 99% 99% 0% 94% 94% 0% 100% 100% 0% 77% 77% 1% 99% 94% 100% 77% 99% 94% 100% 77% 1.4 99% 99% 0% 90% 93% 2% 100% 100% 0% 65% 73% 7% 99% 94% 100% 76% Appendix 1.2 Low IC (0.5) Results with Softening as Stage 3 Treatment Softening Ba AVE SD Ca AVE SD Mg AVE SD Sr AVE SD 99% 88% 93% 78% 0.8 99% 99% 0% 89% 89% 0% 94% 93% 0% 79% 79% 1% 99% 89% 94% 79% 100% 97% 95% 89% Low 1.1 1 100% 100% 0% 97% 97% 0% 95% 95% 0% 89% 89% 0% Sulfation 100% 97% 95% 89% 0.8 100% 100% 97% 100% Hydrolysis 1.2 100% 100% 0% 100% 100% 0% 97% 97% 0% 100% 100% 0% 100% 100% 97% 100% 100% 100% 98% 100% 1.4 100% 100% 0% 100% 100% 0% 98% 98% 0% 100% 100% 0% 100% 100% 98% 100% Appendix 1.3 Medium IC (1) Results with Hydrolysis as Stage 3 Treatment Hydrolysis Ba AVE SD Ca AVE SD Mg AVE SD Sr AVE SD 99% 84% 87% 56% 0.8 99% 99% 0% 84% 84% 0% 87% 86% 2% 56% 56% 0% 99% 84% 84% 56% 99% 84% 100% 56% Med 1.1 1 99% 99% 0% 84% 84% 0% 100% 100% 0% 55% 56% 0% Sulfation 99% 84% 100% 55% 0.9 99% 84% 100% 56% Softening 1.2 99% 99% 0% 84% 84% 0% 100% 100% 0% 56% 56% 0% 99% 84% 100% 55% 99% 85% 100% 56% 1.4 99% 99% 0% 84% 85% 0% 100% 100% 0% 56% 56% 0% 99% 84% 100% 55%

77 Appendix 1.4 Medium IC (1) Results with Softening as Stage 3 Treatment Softening Ba AVE SD Ca AVE SD Mg AVE SD Sr AVE SD 99% 78% 99% 50% 0.8 99% 99% 0% 77% 77% 0% 99% 99% 0% 50% 50% 1% 99% 77% 99% 49% 100% 95% 99% 79% Med 1.1 1 100% 100% 0% 94% 94% 0% 99% 99% 0% 79% 79% 1% Sulfation 100% 94% 99% 78% 0.8 100% 100% 100% 99% Hydrolysis 1.2 100% 100% 0% 100% 100% 0% 100% 100% 0% 99% 99% 0% 100% 100% 100% 99% 100% 100% 100% 100% 1.4 100% 100% 0% 100% 100% 0% 100% 100% 0% 100% 100% 0% 100% 100% 100% 100% Appendix 1.5 High IC (2) Results with Hydrolysis as Stage 3 Treatment Hydrolysis Ba2304 AVE SD Ca1840 AVE SD Mg2802 AVE SD Sr4215 AVE SD 99% 82% 99% 57% 0.8 99% 99% 0% 82% 83% 0% 99% 99% 0% 57% 58% 1% 99% 83% 99% 58% 99% 83% 99% 58% High 2 1 99% 99% 0% 83% 83% 0% 99% 99% 0% 58% 58% 0% 1.1 99% 83% 99% 58% Sulfation 99% 83% 100% 58% 0.9 1.2 99% 99% 0% 83% 83% 0% 99% 99% 0% 58% 58% 0% Softening 99% 83% 99% 58% 99% 86% 99% 58% 1.4 99% 99% 0% 86% 86% 0% 99% 99% 0% 58% 58% 0% 99% 86% 99% 58% Appendix 1.6 High IC (2) Results with Softening as Stage 3 Treatment Softening Ba2304 AVE SD Ca1840 AVE SD Mg2802 AVE SD Sr4215 AVE SD 100% 87% 99% 68% 0.8 100% 100% 0% 88% 88% 0% 99% 99% 0% 71% 70% 1% 100% 88% 99% 70% 100% 100% 100% 100% High 2 1 100% 100% 0% 100% 100% 0% 100% 100% 0% 100% 99% 0% 1.1 100% 100% 100% 99% Sulfation 100% 100% 100% 100% 0.8 1.2 100% 100% 0% 100% 100% 0% 100% 100% 0% 100% 100% 0% Hydrolysis 100% 100% 99% 100% 100% 100% 100% 100% 1.4 100% 100% 0% 100% 100% 0% 99% 99% 0% 100% 100% 0% 100% 100% 99% 100%

78 Appendix 1.7 High IC (4) Results with Hydrolysis as Stage 3 Treatment Hydrolysis Ba Ave SD Ca Ave SD Mg Ave SD Sr Ave SD 98% 89% 61% 57% 0.6 98% 98% 0% 89% 89% 0% 61% 61% 0% 57% 57% 0% 98% 89% 61% 57% 98% 89% 63% 57% 0.7 98% 98% 0% 89% 89% 0% 63% 63% 0% 57% 57% 0% 1.1 Sulfation 98% 89% 64% 57% 0.9 Softening 98% 89% 65% 57% 0.8 98% 98% 0% 89% 89% 0% 65% 65% 1% 57% 56% 0% 98% 89% 64% 56% 98% 89% 69% 56% 1 98% 98% 0% 89% 89% 0% 70% 69% 1% 56% 56% 0% 98% 89% 68% 57% Appendix 1.8 High IC (4) Results with Softening as Stage 3 Treatment Softening Ba Ave SD Ca Ave SD Mg Ave SD Sr Ave SD 97% 55% 100% 42% 0.6 97% 97% 0% 56% 55% 1% 100% 100% 0% 42% 41% 2% 96% 54% 100% 38% 97% 60% 100% 44% 0.7 97% 97% 0% 60% 61% 1% 100% 100% 0% 48% 47% 2% 1.1 Sulfation 97% 61% 100% 49% 0.8 Hydrolysis 97% 69% 100% 55% 0.8 97% 97% 0% 70% 70% 1% 100% 100% 0% 55% 55% 0% 97% 70% 100% 56% 98% 84% 100% 64% 1 98% 98% 0% 85% 84% 1% 100% 100% 0% 64% 64% 0% 98% 84% 100% 63%

79 APPENDIX 2 – KINETICS RESULTS AND SUMMARY STATISTICS

Appendix 2.1.1 Sulfation Stage 1 Low IC (0.5) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Net Weight of Precipitate (g) Percent Removal 600 0.153 0.2328 0.0798 100 300 0.1544 0.2282 0.0738 92.48120301 180 0.1533 0.2274 0.0741 92.85714286 120 0.1518 0.2313 0.0795 99.62406015 60 0.1512 0.225 0.0738 92.48120301 Appendix 2.1.2 Sulfation Stage 1 Low IC (0.5) Optimization Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Net Weight of Precipitate (g) Average Stdev. Percent Removal Average Stdev. 0.1535 0.2307 0.0772 97.43374001 600 0.1523 0.2333 0.081 0.0792333 0.001914 102.2297013 100 2.4156293 0.153 0.2325 0.0795 100.3365587 0.1501 0.226 0.0759 95.79301641 120 0.1522 0.228 0.0758 0.0761 0.0004359 95.6668069 96.04543542 0.5501345 0.1518 0.2284 0.0766 96.67648296 0.1546 0.2273 0.0727 91.75431216 60 0.1545 0.2275 0.073 0.0717667 0.0018824 92.13294068 90.57635675 2.3757354 0.1526 0.2222 0.0696 87.84181742 0.1557 0.2222 0.0665 83.92932268 40 0.1535 0.2112 0.0577 0.0649667 0.0066343 72.82288599 81.99411022 8.37306 0.1511 0.2218 0.0707 89.230122 0.1548 0.215 0.0602 75.97812369 20 0.1523 0.2167 0.0644 0.0642333 0.0039526 81.27892301 81.06857383 4.9886028 0.1571 0.2252 0.0681 85.9486748 Appendix 2.1.3 Sulfation Stage 1 High IC (4) Scoping Results Reaction Time (s) Weight of Filter (g) Weight After Filtration (g) Net Precipitate weight (g) Percent Removal 600 0.1098 0.6175 0.5077 100 300 0.1092 0.5864 0.4772 93.99251526 180 0.1086 0.6035 0.4949 97.47882608 120 0.1115 0.6061 0.4946 97.41973606 60 0.108 0.5542 0.4462 87.88654717 Appendix 2.1.4 Sulfation Stage 1 High IC (4) Optimization Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Net Weight of Precipitate (g) Average Standard Deviation Percent Removal Average Stdev. 0.1091 0.6143 0.5052 99.63841956 600 0.1092 0.6039 0.4947 0.5070333 0.013344787 97.5675498 100 2.6319348 0.1099 0.6311 0.5212 102.7940306 0.1081 0.6136 0.5055 99.69758727 120 0.1087 0.6028 0.4941 0.5114333 0.020940232 97.44921438 100.867793 4.129951826 0.1072 0.6419 0.5347 105.4565775 0.1069 0.6058 0.4989 98.39589771 60 0.1083 0.6064 0.4981 0.5074333 0.015478157 98.23811715 100.0788903 3.052690155 0.107 0.6323 0.5253 103.602656 0.1076 0.612 0.5044 99.48063901 40 0.1072 0.6489 0.5417 0.5061333 0.034732454 106.8371573 99.82249688 6.850132195 0.1072 0.5795 0.4723 93.1496943 0.1076 0.5235 0.4159 82.02616528 20 0.1081 0.5239 0.4158 0.4525667 0.063595152 82.00644271 89.25777398 12.54259782 0.1081 0.6341 0.526 103.740714 Appendix 2.1.5 Hydrolysis Stage 2 Low IC (0.5) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Net. Weight of Precipitate (g) Percent Removal 60 0.1161 0.1584 0.0423 89.8089172 120 0.1179 0.1614 0.0435 92.3566879 180 0.1158 0.1608 0.045 95.54140127 300 0.1168 0.1585 0.0417 88.53503185 600 0.1153 0.1624 0.0471 100

80 Appendix 2.1.6 Hydrolysis Stage 2 Low IC (0.5) Optimization Results Reaction Time (s) Filter Weight (g) After Filtration (g) Weight of Precipitate (g) Average (g) Stdev. Percent Removal Average Stdev. 0.1173 0.1438 0.0265 84.75479744 45 0.118 0.1459 0.0279 0.0274667 0.00084 89.23240938 87.84648188 2.68225 0.1168 0.1448 0.028 89.55223881

0.116 0.1432 0.0272 86.99360341 90 0.1186 0.1472 0.0286 0.0274 0.00111 91.47121535 87.63326226 3.56147 0.1165 0.1429 0.0264 84.43496802

0.1166 0.1479 0.0313 100.1066098 600 0.1168 0.1492 0.0324 0.0312667 0.00115 103.6247335 100 3.6792 0.117 0.1471 0.0301 96.26865672

Appendix 2.1.7 Hydrolysis Stage 2 High IC (4) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Net Weight of Precipitate (g) Percent Removal 60 0.1164 0.4115 0.2951 104.7196593 120 0.1165 0.4007 0.2842 100.8516678 180 0.1168 0.4071 0.2903 103.0163236 300 0.1167 0.4124 0.2957 104.9325763 600 0.1159 0.3977 0.2818 100 Appendix 2.1.8 Hydrolysis Stage 2 High IC (4) Optimization Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Average Stdev. Percent Removal Average Stdev. 0.1166 0.3511 0.2345 110.8048512 45 0.1166 0.3482 0.2316 0.232833333 0.0015 109.4345566 110.0173256 0.70772 0.1144 0.3468 0.2324 109.8125689 0.1178 0.3538 0.236 111.5136242 90 0.1164 0.368 0.2516 0.240933333 0.00925 118.8848638 113.8447 4.369 0.1176 0.3528 0.2352 111.1356119 0.1161 0.3407 0.2246 106.1269491 600 0.1181 0.3177 0.1996 0.211633333 0.01253 94.31406521 100 5.91878 0.1169 0.3276 0.2107 99.55898567 Appendix 2.1.9 Hydrolysis Stage 3 Low IC (0.5) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Percent Removal 60 0.1152 0.1332 0.018 89.10891089 120 0.1159 0.1346 0.0187 92.57425743 180 0.1148 0.1326 0.0178 88.11881188 300 0.1159 0.1336 0.0177 87.62376238 600 0.1153 0.1355 0.0202 100 Appendix 2.2.0 Hydrolysis Stage 3 Low IC (0.5) Optimization Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Average Stdev. Percent Removal Average Stdev. 0.1153 0.1341 0.0188 89.24050633 45 0.1152 0.132 0.0168 0.0178 0.001 79.74683544 84.4937 4.74684 0.1157 0.1335 0.0178 84.49367089 0.1152 0.1339 0.0187 88.76582278 90 0.115 0.1337 0.0187 0.0187333 5.7735E-05 88.76582278 88.9241 0.27406 0.1166 0.1354 0.0188 89.24050633 0.1154 0.1365 0.0211 100.1582278 600 0.1153 0.1359 0.0206 0.0210667 0.000450925 97.78481013 100 2.14047 0.115 0.1365 0.0215 102.056962 Appendix 2.2.1 Hydrolysis Stage 3 High IC (4) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Percent Removal 600 0.1151 0.2414 0.1263 100 300 0.1152 0.2366 0.1214 96.12034838 180 0.1142 0.249 0.1348 106.7300079 120 0.1143 0.2548 0.1405 111.2430721 60 0.1155 0.2482 0.1327 105.0673001

81 Appendix 2.2.2 Hydrolysis Stage 3 High IC (4) Optimization Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Average Stdev. Percent removal Average Stdev. 0.1158 0.2383 0.1225 96.40608604 600 0.1149 0.2402 0.1253 0.1270667 0.0053675 98.60965373 100 4.45489 0.115 0.2484 0.1334 104.9842602 0.1111 0.2373 0.1262 99.31794334 90 0.1152 0.2443 0.1291 0.1275333 0.0036856 101.6002099 100.36726 1.15216 0.1155 0.2428 0.1273 100.1836306 0.1149 0.2569 0.142 111.752361 45 0.1137 0.268 0.1543 0.1477333 0.0055507 121.432319 116.26443 4.87319 0.1157 0.2626 0.1469 115.6086044 Appendix 2.2.3 Softening Stage 2 Low IC (0.5) Scoping Results Reaction Time (s) Filter Weight (g) Weight after Filtration (g) Weight of Precipitate (g) Percent Removal 60 0.1166 0.2076 0.091 108.2045184 120 0.1156 0.2018 0.0862 102.4970273 180 0.1149 0.2012 0.0863 102.6159334 300 0.1149 0.1964 0.0815 96.90844233 600 0.1151 0.1992 0.0841 100 Appendix 2.2.4 Softening Stage 2 Low IC (0.5) Optimization Results Reaction Time (s) Filter Weight (g) Weigh After Filtration (g) Weight of Precipitate (g) Average Stdev. Percent Removal Average Stdev. 0.1147 0.1967 0.082 101.9900498 45 0.1154 0.1902 0.0748 0.07733 0.00405 93.03482587 96.1857 5.032832804 0.1151 0.1903 0.0752 93.53233831 0.1147 0.1934 0.0787 97.88557214 90 0.1143 0.1911 0.0768 0.07707 0.00152 95.52238806 95.8541 1.887653804 0.1152 0.1909 0.0757 94.15422886 0.1161 0.1964 0.0803 99.87562189 600 0.1157 0.1982 0.0825 0.0804 0.00205 102.6119403 100 2.552025439 0.1151 0.1935 0.0784 97.51243781 Appendix 2.2.5 Softening Stage 2 High IC (4) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Percent Removal 60 0.1157 0.7578 0.6421 89.60368406 120 0.1151 0.6578 0.5427 75.73262629 180 0.1154 0.6767 0.5613 78.32821658 300 0.1164 0.6797 0.5633 78.60731231 600 0.1164 0.833 0.7166 100 Appendix 2.2.6 Softening Stage 2 High IC (4) Optimization Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Average Stdev. Percent Removal Average Stdev. 0.1157 0.8815 0.7658 135.7480501 45 0.1151 0.8265 0.7114 0.7044667 0.06508 126.1049397 124.876 11.535853 0.1159 0.7521 0.6362 112.7747577 0.1163 0.7377 0.6214 110.1512645 90 0.1143 0.7371 0.6228 0.6173667 0.00823 110.3994328 109.436 1.4585565 0.1159 0.7238 0.6079 107.7582132 0.1157 0.6801 0.5644 100.0472701 600 0.1155 0.6792 0.5637 0.5641333 0.00038 99.92318601 100 0.0671107 0.1137 0.678 0.5643 100.0295438 Appendix 2.2.7 Softening Stage 3 Low IC (0.5) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Percent Removal 600 0.1152 0.1798 0.0646 100 300 0.1151 0.1828 0.0677 104.7987616 180 0.1155 0.183 0.0675 104.4891641 120 0.1145 0.1785 0.064 99.07120743 60 0.1154 0.1803 0.0649 100.4643963

82 Appendix 2.2.8 Softening Stage 3 Low IC (0.5) Optimization Results Reaction Time (s) Filter Wreight (g) Weight After Filtration (g) Weight of Precipitate (g) Average Stdev. Percent Removal Average Stdev. 0.1159 0.1789 0.063 96.67519182 600 0.1159 0.1815 0.0656 0.06517 0.00199 100.6649616 100 3.04724 0.1145 0.1814 0.0669 102.6598465 0.1144 0.1797 0.0653 100.2046036 90 0.1144 0.1853 0.0709 0.06993 0.00423 108.797954 107.315 6.49657 0.1141 0.1877 0.0736 112.9411765 0.1151 0.192 0.0769 118.0051151 45 0.1149 0.1912 0.0763 0.0764 0.00046 117.084399 117.238 0.70321 0.1155 0.1915 0.076 116.6240409 Appendix 2.2.9 Softening Stage 3 High IC (4) Scoping Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Percent Removal 600 0.1147 0.6223 0.5076 100 300 0.1151 0.6545 0.5394 106.2647754 180 0.1153 0.6243 0.509 100.2758077 120 0.115 0.6419 0.5269 103.8022065 60 0.1163 0.8258 0.7095 139.7754137 Appendix 2.3.0 Softening Stage 3 High IC (4) Optimization Results Reaction Time (s) Filter Weight (g) Weight After Filtration (g) Weight of Precipitate (g) Average Stdev. Percent Removal Average Stdev. 0.1149 0.652 0.5371 101.123384 600 0.116 0.6399 0.5239 0.5311333 0.0066905 98.6381323 100 1.25967 0.1151 0.6475 0.5324 100.2384837 0.116 0.7673 0.6513 122.6245764 90 0.1153 0.804 0.6887 0.6932 0.0443217 129.6661228 130.513 8.34473 0.1153 0.8549 0.7396 139.2494038 0.1152 1.0694 0.9542 179.653571 45 0.1147 0.8183 0.7036 0.8383333 0.1263608 132.4714447 157.839 23.7908 0.1159 0.9731 0.8572 161.3907368

83 APPENDIX 3 – ACID MINE DRAINAGE TREATMENT RESULTS AND

SUMMARY STATISTICS

Appendix 3.1 Acid Mine Drainage Sulfation Treatment Mass Change in Concentration Results- Low IC (0.5) Treatment Ba4554 Average Stdev. Sr4215 Average Stdev. 66% 3% 0.8 63% 63% 3% 2% 2% 1% 60% 1% 65% 1% 0.9 64% 63% 2% 1% 1% 1% 61% 0% 71% 3% Low 0.5 1 70% 70% 1% 1% 2% 1% Sulfation 69% 1% AMD 73% 3% Treatment 1.1 70% 71% 2% 2% 2% 1% 69% 1% 79% 2% 1.2 80% 80% 1% 2% 2% 0% 80% 2% 83% 4% 1.4 85% 84% 1% 3% 4% 0% 84% 4% Appendix 3.2 Acid Mine Drainage Sulfation Treatment Mass Change in Concentration Results- Medium IC (1) Treatment Ba4554 Average Stdev. Sr4215 Average Stdev. 72% 2% 0.8 71% 71% 1% 3% 2% 0% 70% 2% 77% 3% 0.9 76% 77% 1% 1% 2% 1% 76% 3% 84% 6% Medium 1 1 83% 83% 1% 4% 5% 1% Sulfation 83% 4% AMD 89% 9% Treatment 1.1 88% 88% 1% 7% 8% 1% 87% 7% 91% 11% 1.2 91% 91% 0% 11% 11% 1% 91% 12% 95% 15% 1.4 95% 95% 0% 13% 14% 1% 95% 15%

84 Appendix 3.3 Acid Mine Drainage Sulfation Treatment Mass Change in Concentration Results- High IC (2) Treatment Ba4554 Average Stdev. Sr2165 Average Stdev. 70% 8% 0.8 69% 70% 0% 7% 8% 1% 70% 8% 77% 8% 0.9 76% 76% 1% 9% 8% 1% 76% 7% 83% 10% High 2 1 83% 83% 0% 11% 10% 1% Sulfation 82% 9% AMD 88% 13% Treatment 1.1 88% 88% 1% 12% 12% 2% 87% 9% 91% 15% 1.2 90% 91% 1% 14% 14% 1% 92% 14% 95% 17% 1.4 94% 94% 0% 15% 16% 1% 95% 16% Appendix 3.4 Acid Mine Drainage Sulfation Treatment Mass Change in Concentration Results- High IC (4) Treatment Ba4554 Average Stdev. Sr2165 Average Stdev. 76% 0% 0.8 74% 74% 20% 0% 0% 1% 73% 0% 83% 0% 0.9 82% 82% 1% 0% 0% 1% 82% 0% 90% 0% High 4 1 89% 90% 0% 0% 0% 1% Sulfation 89% 0% AMD 96% 2% Treatment 1.1 95% 95% 0% 1% 1% 1% 95% 0% 98% 4% 1.2 98% 98% 0% 2% 3% 1% 98% 3% 99% 5% 1.4 99% 99% 0% 4% 4% 1% 99% 4%

85 Appendix 3.5 Acid Mine Drainage Sulfation Treatment Percent Change in Concentration Results- Low IC (0.5) Ba4554 Average Stdev. Ca3179 Average Stdev. Mg2795 Average Stdev. Sr2165 Average Stdev. 75% 34% 21% 29% 0.8 73% 73% 2% 33% 33% 1% 20% 20% 1% 29% 28% 1% 71% 32% 19% 28% 75% 34% 21% 30% 0.9 75% 74% 1% 35% 34% 0% 21% 21% 0% 30% 30% 1% 72% 34% 20% 29% 80% 37% 23% 33% Low IC 1 80% 80% 1% 36% 36% 1% 21% 22% 1% 32% 33% 1% Sulfation 79% 36% 21% 32% AMD 82% 38% 23% 35% Treatment 1.1 80% 81% 1% 38% 38% 0% 23% 23% 1% 35% 35% 1% 79% 38% 22% 34% 86% 40% 24% 37% 1.2 87% 87% 0% 38% 39% 1% 23% 25% 1% 37% 37% 0% 87% 39% 23% 37% 90% 42% 26% 41% 1.4 91% 90% 1% 42% 42% 0% 26% 26% 0% 41% 41% 0% 90% 42% 27% 42% Appendix 3.6 Acid Mine Drainage Sulfation Treatment Percent Change in Concentration Results- Medium IC (1) Ba4554 Average Stdev. Ca1840 Average Stdev. Mg2795 Average Stdev. Sr4215 Average Stdev. 84% 43% 35% 45% 0.8 83% 84% 0% 43% 43% 0% 36% 36% 0% 45% 45% 0% 83% 43% 36% 45% 88% 45% 38% 48% 0.9 87% 88% 0% 44% 44% 1% 37% 37% 1% 47% 47% 0% 87% 45% 37% 48% 92% 48% 41% 52% Medium IC 1 91% 92% 0% 46% 47% 1% 40% 40% 1% 51% 51% 0% Sulfation 91% 46% 40% 51% AMD 95% 50% 44% 56% Treatment 1.1 94% 94% 0% 50% 49% 0% 43% 43% 1% 54% 55% 1% 94% 49% 43% 55% 96% 52% 46% 58% 1.2 96% 96% 0% 50% 51% 1% 45% 46% 0% 58% 59% 0% 96% 51% 46% 59% 98% 56% 50% 64% 1.4 98% 98% 0% 54% 55% 1% 48% 49% 1% 63% 63% 1% 98% 54% 49% 63%

86 Appendix 3.7 Acid Mine Drainage Sulfation Treatment Percent Change in Concentration Results- High IC (2) Ba4554 Average Stdev. Ca1840 Average Stdev. Mg2795 Average Stdev. Sr4215 Average Stdev. 87% 54% 50% 59% 0.8 86% 87% 0% 53% 54% 0% 50% 50% 0% 59% 59% 0% 87% 54% 50% 59% 90% 57% 53% 62% 0.9 90% 90% 0% 56% 56% 1% 52% 52% 1% 62% 62% 0% 90% 56% 52% 62% 94% 59% 55% 65% High 2 1 93% 93% 0% 59% 59% 0% 55% 55% 0% 65% 65% 0% Sulfation 93% 58% 55% 65% AMD 96% 62% 58% 68% Treatment 1.1 95% 95% 0% 61% 61% 1% 58% 58% 1% 68% 68% 1% 95% 60% 57% 67% 97% 64% 60% 70% 1.2 97% 97% 0% 64% 64% 0% 59% 60% 0% 70% 70% 0% 97% 64% 60% 70% 98% 67% 63% 74% 1.4 98% 98% 0% 66% 67% 1% 62% 63% 1% 73% 74% 0% 98% 67% 63% 74% Appendix 3.8 Acid Mine Drainage Sulfation Treatment Percent Change in Concentration Results- High IC (4) Ba4554 Average Stdev. Ca3179 Average Stdev. Mg2795 Average Stdev. Sr2165 Average Stdev. 93% 72% 70% 73% 0.8 93% 93% 0% 72% 72% 0% 70% 70% 0% 72% 72% 0% 93% 71% 69% 72% 96% 74% 72% 75% 0.9 95% 96% 0% 74% 74% 0% 71% 72% 0% 75% 75% 0% 95% 73% 71% 74% 98% 76% 74% 77% High 4 1 98% 98% 0% 75% 75% 0% 73% 73% 0% 76% 77% 0% Sulfation 98% 75% 73% 77% AMD 99% 77% 75% 79% Treatment 1.1 99% 99% 0% 77% 77% 0% 75% 75% 0% 79% 79% 0% 99% 77% 74% 78% 100% 79% 76% 81% 1.2 100% 100% 0% 79% 79% 0% 76% 76% 0% 80% 80% 0% 99% 79% 76% 80% 100% 81% 79% 83% 1.4 100% 100% 0% 81% 81% 0% 78% 78% 0% 83% 83% 0% 100% 81% 78% 83%

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