Chemical and Geological Controls on the Composition of Waters And

Chemical and Geological Controls on the Composition of Waters and

Sediments in Streams Located within the Western Allegheny Plateau:

The Shade River Watershed

A thesis presented to

the faculty of

the College of Arts and Sciences of Ohio University

In partial fulfillment

of the requirements for the degree

Master of Science

Prosper Gbolo

June 2008 2

This thesis titled

Chemical and Geological Controls on the Composition of Waters and

Sediments in Streams Located within the Western Allegheny Plateau:

The Shade River Watershed

PROSPER GBOLO

has been approved for

the Department of Geological Sciences

and the College of Arts and Sciences by

Dina L. Lopez

Professor of Geological Sciences

Benjamin M. Ogles

Dean, College of Arts and Sciences

ABSTRACT

GBOLO, PROSPER, M.S., June 2008, Geological Sciences

Chemical and Geological Controls on the Composition of Waters and

Sediments in Streams Located within the Western Allegheny Plateau:

The Shade River Watershed (222 pp.)

Director of Thesis: Dina L. Lopez

The Western Allegheny Plateau Ecoregion (WAP) and Shade

River Watershed in SE Ohio were investigated to determine the

chemical composition of waters and sediments, and their relationship

with geology, land-use and biological indices. Ninety-three sites

were sampled within the WAP with twenty-two sites in the Shade

River. Chemical concentration of the waters in the Shade River fell

within the USEPA criteria for the protection of aquatic life except

DO, iron, manganese and phosphate while the causes of impairment

within the WAP included pH, DO, EC, alkalinity, phosphate, iron,

manganese, nitrate and sulfate. The waters were Ca-HCO3 dominated with weathering being the main process controlling the water chemistry. Biological indicator such as Index of Biotic Integrity

(fish) was sensitive to PO4 , Na, K, Ca, Mg, Cl and DO while

Invertebrate Community Index (macroinvertebrate) correlated with

pH, acidity and DO. Periphyton Index of Biotic Integrity (algae)

showed no relationship with water chemistry.

Approved: ______

Dina L. Lopez

Professor of Geology

ACKNOWLEDGMENTS

I would like to express my deep and sincere gratitude to my advisor, Dr. Dina Lopez, for her guidance, help and encouragement throughout my stay in Ohio University. Her knowledge has been the basis for this thesis.

I would also like to show my appreciation to members of my thesis committee, consisting of Dr. Greg Nadon, Dr. Keith Milam and my advisor for their excellent advice, comments and constructive criticism.

I am grateful to my field assistants Josh Coe, Ashley

Campbell, and Shannon Cook for their help, understanding and tolerance in the field.

Support for this work was provided through by a United States

Environmental Protection Agency (USEPA) grant from the Science To

Achieve Results (STAR) project.

TABLE OF CONTENTS

Page

ABSTRACT ...... 3

ACKNOWLEDGMENTS ...... 5

LIST OF TABLES ...... 12

LIST OF FIGURES ...... 15

CHAPTER ONE: INTRODUCTION ...... 22

1.0 Introduction ...... 22

1.1 Objectives ...... 27

1.2 Significance...... 27

1.3 Reclamation laws ...... 29

1.3.1 National Environmental Protection Act (NEPA), 1969 ...... 29

1.3.2 Clean Water Act (CWA), 1972 ...... 30

1.3.3 Surface Mining Control and Reclamation Act (SMCRA), 1977 ..... 31

1.3.4 Ohio legislation ...... 33

1.4 Biological Indicators ...... 34

1.4.1 Index of Biotic Integrity ...... 34

1.4.2 Invertebrate Community Index ...... 35

1.4.3 Periphyton Index of Biotic Integrity (PIBI) ...... 35

CHAPTER TWO --- STUDY AREA ...... 36

2.0 Site Description ...... 36

2. 1 Climate ...... 38

2.2 Topography ...... 40

2.3 Geology ...... 40

2.4 Soils...... 44

2.5 Land use and land cover ...... 47

2.6 WAP Groundwater Hydrology ...... 49

CHAPTER THREE --- BACKGROUND ...... 51

3.0 Introduction ...... 51

3.1 Bedrock Geology ...... 51

3.2 Soil Types and Sediments ...... 52

3.3 Climate ...... 53

3.4 Land Use ...... 54

3.5 Urbanization or Anthropogenic Input ...... 56

3.6 Summary of the Chemistry of Phase I (2005 data) ...... 56

CHAPTER FOUR--- METHODOLOGY ...... 60

4.0 Methodology ...... 60

4.1 Selection of Sampling Points ...... 60

4.2 Field Parameters ...... 63

4.3 Streambed Sediment Samples for Cations Analyses ...... 66

4.4 Streamwater Samples for Cations and Anions Analyses ...... 67

4.4.1 Filtered Samples...... 68

4.4.2 Unfiltered Samples ...... 69

4.5 Laboratory Work ...... 70

4.5.1 Sediment Samples Analyses ...... 70

4.5.1.1 Sediment Organic Matter Determination ...... 71 4.5.1.2 Sediment Cation Determination ...... 71

4.5.2 Water Samples Analyses ...... 73

4.5.2.1 Cations ...... 73 4.5.2.2 Anions ...... 74 4.6 GIS Processing of Data ...... 79

4.7 Cation–Anion Balances (Error Calculation for the Streamwater Chemistry) 80

CHAPTER FIVE---RESULTS ...... 81

5.0 Results ...... 81

5.1 Streamwater Chemistry ...... 81

5.1.1 Field parameters ...... 81

5.1.1.1 pH ...... 81 5.1.1.2 Temperature ...... 84 5.1.1.3 Dissolved Oxygen (DO) ...... 84 5.1.1.4 Total Dissolved Solids (TDS) ...... 87 5.1.1.5 Electric Conductivity ...... 89 5.1.1.6 Alkalinity ...... 91 5.1.1.7 Acidity...... 92 5.1.2 Anions ...... 94

5.1.2.1 Nitrate ...... 94 5.1.2.2 Sulfate ...... 96 5.1.2.3 Total Phosphate ...... 98 5.1.2.4 Chloride...... 100 5.1.3 Streamwater cations ...... 102

5.1.3.1 Major cations ...... 102 5.1.3.2 Trace Elements ...... 110 5.2 Streambed Sediment Chemistry ...... 116

5.2.1 Sodium ...... 116

5.2.2 Potassium ...... 117

5.2.3 Magnesium ...... 117

5.2.4 Calcium ...... 117

5.2.5 Iron ...... 118

5.2.6 Manganese ...... 118

5.2.7 Aluminum ...... 119

5.2.8 Other Elements ...... 119

5.3 Total Organic Carbon (TOC) ...... 120

5.4 Stream Discharge Rate (Flow) ...... 120

CHAPTER SIX--- DISCUSSION ...... 152

6.0 Introduction ...... 152

6.1 Analysis of the Spatial Variations for the Chemical Entities within the WAP

Ecoregion and the Shade River Watershed ...... 152

6.1.1 Field Parameters ...... 152

6.1.2 Anions ...... 154

6.1.3 Cations ...... 155

6.2 Composition of the Streamwaters in the WAP and Shade River Watershed 157

6.3 Factors Controlling Water Quality within the WAP Ecoregion and the Shade

River Watershed...... 158

6.3.1 Rock Weathering ...... 158

6.3.2 Nutrients ...... 162

6.3.3 Mining ...... 163

6.4 Statistical Analysis of the Chemical Species within the Streamwater Samples

in the WAP Ecoregion ...... 164

6.5 Statistical Analysis of the Chemical Species within the Streamwater Samples

in the Western and Middle Branches of Shade River Watershed ...... 167

6.6 Streambed Sediment Chemistry within the WAP Ecoregion ...... 167

6.7 Streambed Sediment Chemistry of the Samples within the Shade River

Watershed ...... 170

6.8 Relationship between TOC and Streambed Sediment Chemistry in the WAP

...... 171

6.9 Distribution Coefficient between the Chemical Species in the Streambed

Sediments and Streamwaters in the WAP Ecoregion ...... 172

6.10 Relationship between Sediment and Water Chemistry ...... 172

6.11 Relationship between PIBI and Water Chemistry ...... 174

6.12 Relationship between IBI and the Water Chemistry...... 175

6.13 Relationship between ICI and Water Chemistry ...... 176

6.14 Relationship between the Biological Indices and Sediment Chemistry ..... 176

CHAPTER SEVEN--- CONCLUSIONS AND RECOMMENDATIONS ...... 199

7.0 Conclusions ...... 199

7.1 Recommendations ...... 202

REFERENCES ...... 205

APPENDIX A: DESCRIPTIVE STATISTICS OF OTHER ELEMENTS IN THE

WATER AND SEDIMENT SAMPLES ...... 214

A.1. Barium ...... 214

A.2. Strontium ...... 214

A.3. Silica...... 215

A.4. Ammonia ...... 215

A.5. Lithium ...... 216

A.6. Cobalt ...... 216

A.7. Chromium ...... 216

A.8. Copper ...... 217

A.9. Nickel ...... 217

A.10. Strontium ...... 218

A.11. Zinc ...... 218

APPENDIX B ...... 219

LIST OF TABLES

Page

Table 2-1 General Stratigraphy of the rocks in the Hocking

Basin…………………………………………………………….……..41

Table 4–1 Field parameters and their units of measurement…………...65

Table 5–1 Physical and field parameters measured in the

WAP ecoregion (Summer 2005 and 2006)………………………..128

Table 5–2 Concentration of some chemical species measured in

the filtered water samples…………………………………………..132

Table 5–3 Concentrations of the trace elements measured in

the Shade River Watershed………………………………………....136

Table 5–4 Concentration of the chemical species measured in

the unfiltered water samples within the WAP ecoregion……….137

Table 5–5 Concentrations of the trace elements measured in

the unfiltered water samples taken from the Shade River

Watershed……………………………………………………………..141

Table 5–6 Descriptive statistics for the measured ions

(filtered samples) and the field parameters with their

respective criterion for aquatic life ( WAP ecoregion)…….……142

Table 5–7 Descriptive statistics for the measured ions (filtered

samples) and the field parameters with their respective criterion

for aquatic life (Shade River Watershed)………………………….143

Table 5–8 Concentration of the elements analyzed within the

sediment samples and the organic content (WAP)…………….....144

Table 5–9 Descriptive statistics for the streambed sediments

taken within WAP………………………………………………….....148

Table 5–10 Descriptive statistics for the streambed sediments

taken within Shade River Watershed……………………………..148

Table 5–11 Measured values for the biological indicators and

the discharge rate for the streams within the WAP ecoregion,

summer 2005 and 2006. These data were collected by the fish,

macroinvertebrate, algae and hydrology teams of the STAR

project…………………………………………………………………149

Table 5–12 Descriptive statistics for the biological indices and

flow rate in the WAP Ecoregion…………………………………...151

Table 6–1 Correlation matrices for chemical species within the

filtered water samples for the WAP ecoregion…………………..178

Table 6–2 Correlation matrices for waters and field parameters

within the Shade River Watershed…………………………………179

Table 6–3 Correlation matrices for chemical species within the

sediment samples for the WAP ecoregion………………….……..180

Table 6–4 Correlation matrices for chemical species within the

sediment samples for the Shade River Watershed. .……………..181

Table 6–5 Distribution Coefficient (mL/g) of some chemical

species measured within sediment and water samples

in the WAP Ecoregion…………………………………….…………182

Table 6–6 Descriptive Statistics for the distribution coefficient

for the cations (mL/g) within the WAP samples……………..….186

Table 6–7 Pearson’s correlation coefficient (r) for the cations

within the stream water (ppm) and streambed sediments in

the WAP Ecoregion ……………………………….…….…………..186

Table 6–8 Pearson’s correlation coefficient between water

chemical species and the PIBI metrics………………………….…187

Table 6–9 Pearson’s correlation coefficient between sediment

chemical species, TOC and the PIBI metrics…………………….188

Table 6–10 Regression statistics for building a model in determining

the ICI equation for the water samples………………………….…189

Table 6–11 Analysis of variance (ANOVA) for the model that

predicted the equation for the ICI…………………………….……189

Table 6–12 Correlation matrices for chemical species within the

filtered water samples (mg/L) and the biological indices

within the WAP ecoregion……………………………………..……190

Table 6–13 Correlation matrices for the chemical species in the

streambed sediment samples (mg/Kg) and the biological

indices within the WAP ecoregion…………………………………190

LIST OF FIGURES

Figure 1-1 Map of Ohio showing the Shade River Watershed

within Athens and Meigs Counties………………………………….28

Figure 2-1 Location of the study area in Ohio..…………………………..36

Figure 2-2 Location of the Shade River Watershed and its

Surrounding sub-watersheds……………………………………...….37

Figure 2-3 Map showing the West and Middle branches of the

Shade River Watershed……………………………………………..…38

Figure 2-4. Map of Ohio showing the geology of the WAP

Ecoregion………………………………………………………..……...43

Figure 2-5 Map of Ohio showing the different Soil Associations...... 46

Figure 2-6 Land use and land cover within Athens and Meigs

Counties………………………………………………………………….48

Figure 2-7 Drainage map of the various creeks within the WAP

ecoregion showing the mainstems of the Shade River

Watershed………………………………………………………....…….50

Figure 3-1 Gibbs diagram for the 2006 summer data…………….…..…..57

Figure 4-1 Map showing the ninety– three sites sampled in the

WAP during summer 2005 and 2006………………………………...61

Figure 4-2 Sampled sites within the West and Middle branches of

the Shade River, summer 2006……………………………………….62

Figure 5-1 Spatial distribution of the measured pH within the

WAP Ecoregion……………………………………………….……….83

Figure 5-2 Spatial distribution of the measured pH within the

Shade River Watershed……………………………………………….83

Figure 5-3 Spatial distribution of the measured DO within the

streams in the WAP ecoregion………………………………….…..86

Figure 5-4 Spatial distribution of the measured DO within the

Shade River Watershed……………………………………………….86

Figure 5-5 Spatial distribution of the measured TDS within

the WAP ecoregion…………………………………………………...88

Figure 5-6 Spatial distribution of the measured TDS within

the Shade River Watershed…………………………………….…….88

Figure 5-7 Spatial distribution of the measured EC within the

WAP ecoregion…………………………………………………………90

Figure 5-8 Spatial distribution of the measured EC within the

Shade River Watershed………………………………………………..90

Figure 5-9 Spatial distribution of the measured acidity within the

WAP ecoregion…………………………………………………………93

Figure 5-10 Spatial distribution of the measured acidity

within the Shade River Watershed…………………………………..93

Figure 5-11 Spatial distribution of the measured nitrate

concentration within the WAP ecoregion……………………..……95

Figure 5-12 Spatial distribution of the measured nitrate within the

Shade River Watershed………………………………………….…….95

Figure 5-13 Spatial distribution of the measured sulfate

concentration within the WAP ecoregion…………………...………97

Figure 5-14 Spatial distribution of the measured sulfate

concentration in the Shade River Watershed………………….……97

Figure 5-15 Spatial distribution for total phosphate concentration

within the WAP ecoregion………………………………………….…99

Figure 5-16 Spatial distribution of the measured total phosphate

concentration in the Shade River Watershed…………….…..….…99

Figure 5-17 Spatial distribution of the measured chloride

concentration in the WAP ecoregion…………………….…………101

Figure 5-18 Spatial distribution of the measured chloride

concentration in the Shade River Watershed……………….……..101

Figure 5-19 Spatial distribution of the measured sodium

concentration in the WAP ecoregion………………………..……..103

Figure 5-20 Spatial distribution of the measured sodium

concentration in the Shade River Watershed……………………..103

Figure 5-21 Spatial distribution of the measured potassium

concentration within the WAP ecoregion…………………………105

Figure 5-22 Spatial distribution of the measured potassium

concentration in the Shade River Watershed……………………..105

Figure 5-23 Spatial distribution of the measured calcium

concentration within the WAP ecoregion………………………….107

Figure 5-24 Spatial distribution of the measured calcium

concentration in the Shade River Watershed……………………..107

Figure 5-25 Spatial distribution of the measured magnesium

concentration in the WAP ecoregion………………………………109

Figure 5-26 Spatial distribution of the measured magnesium

concentration in the Shade River Watershed……………………..109

Figure 5-27 Spatial distribution of the measured iron

concentration in the WAP ecoregion………………………………111

Figure 5-28 Spatial distribution of the measured iron

concentration in the Shade River Watershed……………………..111

Figure 5-29 Spatial distribution of the measured manganese

concentration within the WAP ecoregion………………………….113

Figure 5-30 Spatial distribution of the measured manganese

concentration within the Shade River Watershed………………...113

Figure 5-31 Spatial distribution of the measured aluminum

concentration within the WAP ecoregion………………………….115

Figure 5-32 Spatial distribution of the measured aluminum

concentration within the Shade River Watershed………………...115

Figure 5-33 Spatial distribution of the measured sodium

concentration in sediments within the WAP ecoregion………….121

Figure 5-34 Spatial distribution of the measured sodium

concentration in sediments within the Shade River

Watershed……………………………………………………………..121

Figure 5-35 Spatial distribution of the measured potassium

concentration in sediments within the WAP ecoregion……….…122

Figure 5-36 Spatial distribution of the measured potassium

concentration in sediments within the Shade River

Watershed…………………………………………………………...... 122

Figure 5-37 Spatial distribution of the measured magnesium

concentration in sediments within the WAP ecoregion……….…123

Figure 5-38 Spatial distribution of the measured magnesium

concentration in sediments within the Shade River

Watershed………………………………………………………….….123

Figure 5-39 Spatial distribution of the measured calcium

concentration in sediments within the WAP ecoregion……….…124

Figure 5-40 Spatial distribution of the measured calcium

concentration in sediments within the Shade River

Watershed……………………………………………………………..124

Figure 5-41 Spatial distribution of the measured iron

concentration in sediments within the WAP ecoregion….………125

Figure 5-42 Spatial distribution of the measured iron

concentration within sediments in the Shade River

Watershed………………………………………………………..……125

Figure 5-43 Spatial distribution of the measured manganese

concentration in sediments within the WAP ecoregion………….126

Figure 5-44 Spatial distribution of the measured manganese

concentration in sediments within the Shade River

Watershed……………………………………………………………..126

Figure 5-45 Spatial distribution of the measured aluminum

concentration in sediments within the WAP ecoregion………….127

Figure 5-46 Spatial distribution of the measured aluminum

concentration in sediments within the Shade River

Watershed……………………………………………………………..127

Figure 6-1. Ternary diagrams for the concentrations of the

dominant ions in waters collected within the WAP

Ecoregion………………………………………………………….…..191

Figure 6-2. Ternary diagram for the of the dominant cations

in waters collected within the western and middle branches

of the Shade River Watershed…………………………….………...191

Figure 6-3. Phase diagram for the saturation field of calcite for

the waters within the WAP Ecoregion using 2005 data………....192

Figure 6-4. Stability field of calcite and dolomite for the waters

within the WAP Ecoregion……………………………….………….192

Figure 6-5. Stability field of calcite and dolomite for the waters

within the Shade River Watershed………………………………....193

Figure 6-6. Diagram for the dominant process controlling the

water chemistry in the WAP Ecoregion…………………………...193

Figure 6-7. Diagram for the dominant process controlling the

water chemistry in the western and middle branches of Shade

River Watershed………………………………………………….…..194

Figure 6-8. Diagram of total phosphate against nitrate…………………194

Figure 6-9. Variation in the concentrations of calcium and

magnesium for the waters in the WAP Ecoregion………………..195

Figure 6-10. Variation in the concentrations of calcium and

magnesium for the waters in the Shade River Watershed…..…..195

Figure 6-11. Variation in the concentration of Ca in the streambed

sediment and the stream water in the WAP Ecoregion…………..196

Figure 6-12. Variation in the concentration of Ca in the streambed

sediment and the stream water in the Shade River Watershed….196

Figure 6-13. Variation in the concentration of Mg in the sediment

and the water in the WAP Ecoregion…………………………..…..197

Figure 6-14. Variation in the concentration of Mg in the sediment

and the water in the Shade River Watershed………………….…..197

Figure 6-15. Map of the location of underground mines within

Ohio…………………………………………………………………….198

CHAPTER ONE: INTRODUCTION

1.0 Introduction

Ohio is a state rich in water resources with more than 29,000 miles of named and designated rivers and streams, a 451 mile border on the Ohio River, as well as more than 450 lakes, ponds, and reservoirs that cover more than 188,000 acres (Rankin et al., 1996). However, most of these water bodies have been impaired by human activities such as industrialization, urbanization, agriculture, mining, road construction and timber harvesting creating instability in the ecosystems.

Most of the environmental problems facing Ohio today result from urbanization and industrialization. During the pre–industrial era, the cities had relatively small populations with low levels of pollution and environmental problems. The industrial era cities experienced new environmental challenges posed by rapid large–scale industrialization and urbanization (Wang, 2003), which include health problems, waste generation and disposal, pollution, urban sprawling and paving.

Although some of the problems in urban environment have changed dramatically over the last thirty years (Kaplan et. al., 2001), extensive urbanization has affected the geomorphology and hydrology of streams, and adversely affected aquatic communities (Burton et al., 2005).

Agriculture contributed about $68 billion to the economy in 1997

(Kaplan et. al., 2001; Ohio Department of Agriculture, 2001) and it is one of the largest and most dispersed economic activities in Ohio

(Rankin et al., 1996). Agriculture has been the historic root of this nation but the problems associated with agriculture are not new (Dufour et. al., 2001). Currently, urbanization is second only to agriculture as the main cause of stream impairment (Burton et al., 2005). It is estimated that agriculture is responsible for up to 60% of the impaired rivers miles and half to the impaired lake acreage in the United States

(USEPA, 1997). Most of the environmental degradation in Ohio is linked with agricultural practices such as animal husbandry, grazing, plowing, pesticide spraying, irrigation, fertilizing, planting, and harvesting. Livestock grazing affects components of aquatic systems such as streamside vegetation, stream channel morphology, shape and quality of the water column, and structure of the soil portion of the stream along the bank of the stream (Drewes, 1984). Farmers use high dosages of nutrients (fertilizers) for plants or livestock to accelerate their growth but most of the fertilizers run into streams after a heavy rain (Rankin et al., 1996).

Ohio is endowed with important natural resources such as coal, alluvial gold, oil, gas, limestone, clay, sand, and gravels (Carlson,

1991). Mining of these resources has resulted into several levels of environmental pollution and land degradation. Mining of industrial

24 minerals and coal, and the presence of abandoned mines have caused problems including acid mine drainage (AMD), accidental or intended release of chemicals due to mining operations, subsidence, erosion, sedimentation and/or siltation, which affects the quality of streams. In

Ohio, most of the rocks, especially coal, are associated with high sulfur content which undergo oxidation in the presence of water to form AMD.

This is characterized by low pH and high acidity due to dissolved metals, excessive suspended solids, excessive siltation and elevated concentrations of dissolved chemical species such as zinc, iron and aluminum. These elements are toxic to the respiratory tract of fish and other aquatic organisms (Boult et al., 1993; Henrot and Weider, 1990;

Stoertz et al., 2002).

Studies of fish and macroinvertebrate communities, habitats, and a number of hydrochemical parameters in the Monday Creek Watershed in Ohio, for example, show that AMD eliminated fish communities and severely limited macroinvertebrate communities indirectly affected tributaries (Stoertz et al., 2002). These tributaries have poor water quality, support no fish communities, and have low–diversity macroinvertebrate communities.

Aquatic invertebrates are sensitive to subtle changes in water quality. Consequently, they have been extensively examined as indicators of pollution (Larimore, 1974). The population of the invertebrates can be used to delineate areas of pollution within a

25 stream. The bottom dwelling (benthic) invertebrates are directly affected by any form of pollution that enters their habitat. The pollutants that move in streams are adsorbed onto the streambed sediments thereby affecting the interactions between the streambed sediments, stream water, and the aquatic organisms. Therefore, it is important to monitor the chemical properties of both the streambed sediments and the stream water and then compare them to the biological indicators. This is important because recent studies have shown that biological impact from non–point sources and habitat degradation cannot be measured by considering only the physical and chemical characteristics of the water bodies (Wang, 2001).

Currently, the United States Environmental Protection Agency

(USEPA) is embarking on a program to monitor the quality of the various watersheds and classify them according to the chemical, hydrological, geomorphological, and biological gradient conditions.

These factors are very important for the sustainability of the aquatic environment and any variations in these parameters can have adverse effect on the quality of water, and the physicochemical and biologic components of the stream.

Ohio University, through the Voinovich School for Leadership and Public Affairs, was awarded a grant under the Science To Achieve

Result (STAR) program to develop a watershed classification system and geomorphic tool to predict habitat variables in the Western

Allegheny Plateau (WAP) Ecoregion. The purpose of this grant is refining biological criteria and stressor identification of impaired streams (STAR, 2006). This work is a multi-disciplinary research involving water geochemistry, biology, geomorphology, hydrology, geography, and geographic information system.

The STAR research work is divided into three phases. Phase I involved developing a classification system to explain variations in reference biological assemblages and the physical and chemical conditions in wadable reference streams within the ecoregion. In this phase, reference sites were used in stream classification so that a strong pattern with geomorphic variables and abiotic factors could be developed (STAR, 2006). The main aim of this phase was to ascertain the relationship between some geomorphic variables and their influence on biological classifications. Phase II involves the development of geomorphic model that predicts the habitat quality for second to fifth order streams. Phase III focuses on the identification of the major stressors in the data from the two previous phases, and constructs a model for stressor and response variables for each classifying system

(STAR, 2006).

1.1 Objectives

This thesis focuses on the chemical aspect of Phase II of the STAR project, which compliments the study established by Amaning (2006),

who collected and analyzed samples for the Phase I. In this second

phase, sampling and analysis for the whole WAP was completed by the

writer but a high density of the samples was collected within the Shade

River Watershed. The purpose of the intensive study of the Shade River

was to calibrate a model to be elaborated on in phase III.

The main objectives of this study are: 1) to study the geological

factors controlling stream water and sediment chemistry; 2) to

understand the spatial distribution of stream and sediment chemistry,

and the mineral stability of the dominant ions in the area; 3) to identify

the possible inorganic contaminants that are affecting the aquatic

systems in the WAP and Shade River Watershed; and 4) to investigate

possible correlation between water and sediment chemistry and

biological indicators of stream health. The biological indicators were

investigated by other scientists of the STAR project team.

1.2 Significance

Coal mining is the most important economic activity that provides

energy and employment to many people in Ohio (Dickman, 1965).

However, in Ohio, this economic mineral has sulfide minerals which

react with water in the presence of air to produce acid mine drainage

(AMD). AMD moves along the streams killing aquatic organism and

affecting water quality. A second problem is that, after mining, the

acidic mine spoils are eroded into streams causing siltation.

Catchment

Figure 1-1 Map of Ohio showing the Shade River Watershed within Athens and Meigs Counties.

Before the 1970s, mined lands were not properly reclaimed.

Mining companies abandoned old mines and relocated to new places to

continue the mining activities. This affected the quality of air and

water, which posed high health hazards. Due to these hazards and many

others, some laws were enacted to protect the quality of air, water,

29 land, aquatic life and humans. These laws include the Clean Water Act, the National Environmental Protection Act, and the Surface Mining

Control and Reclamation Act.

1.3 Reclamation laws

These are state and federal laws and regulations enacted for the protection of the environment and control the activities of mining companies. These laws also ensure the protection of waters resources and the safety of the public. These laws include the National

Environmental Protection Act, Clean Water Act, Surface Mining

Control and Reclamation Act and Strip Coal Mine Act.

1.3.1 National Environmental Protection Act (NEPA), 1969

NEPA was enacted in 1969 for the protection of the environment and subsequently was amended in 1975 and 1982. This act established and outlined new policies to govern the use of the environment, and set up a council or federal agencies to protect the quality of the environment (NEPA, 1969). The purposes of this Act were: 1) to declare a national policy which will encourage productive and enjoyable harmony between man and his environment; 2) to promote efforts which will prevent or eliminate damage to the environment and biosphere and stimulate the health and welfare of man; 3) to enrich the understanding of the ecological systems and natural resources important

30 to the Nation; 4) and to establish a Council on Environmental Quality

(NEPA, 1969).

Under NEPA, federal agencies analyze and disclose impacts on major actions on the environment using environmental assessment and environmental impact statements. Since the enactment of NEPA, many environmental laws have been enacted to prevent or minimize human effects on the environment. These include the Clean Air Act (CAA),

Clean Water Act (CWA), and the Safe Drinking Water Act (SDWA), the

Federal Land Management and Policy Act (FLPMA), the Surface

Mining Control and Reclamation Act (SMCRA), the Forest Service

Organic Act, and etc.

1.3.2 Clean Water Act (CWA), 1972

The CWA is a comprehensive statute aimed at restoring and maintaining the quality of the nation’s waters with regards to the chemical, physical and biological components of the waters. This act, which is also known as the Federal Water Pollution Control Act, was enacted in 1972 with subsequent amendments in 1977, 1981, 1987 and

2002. The main aims of this act are: 1) to eliminate or reduce the discharge of pollutant (point and non–point) into navigable waters without permission; 2) maintain water quality for the protection of aquatic and wildlife; and 3) conserve waters for public water supplies, for recreational purpose and for agricultural or industrial use (CWA,

1972). The act has made it unlawful for any person or organization to discharge any pollutant into navigable waters without permission.

Violation of this act could result in criminal or civil liability. The primary authority for the enforcement and the implementation of the act is the USEPA.

Under this act USEPA is authorized to establish criteria and standards for water quality for all the states. The act, through grant programs, has funded the construction of sewage or wastewater treatment plants and also funded educational programs concerning the problems posed by non-point source pollution (CWA, 1972).

1.3.3 Surface Mining Control and Reclamation Act (SMCRA), 1977

Mining and abandoning of mines has resulted in problems associated with deforestation, air pollution, and acid mine drainage. These activities affect the quality of air, surface and groundwater, and land.

In 1977, the United States Congress passed the Surface Mining Control and Reclamation Act (SMCRA) to control mining operations and protect the environment and human health. This federal law was subsequently amended in 1978, 1982, 1984, 1986, 1987, 1990 and 1992. The aims of

SMCRA include protection of the society and the environment from the adverse effects of surface mining and reclamation of land after mining

(SMCRA, 1977). In the case of coal mining, this act insures that enough coal is provided for the sustenance of the economy, and also

32 creates a balance between the protection of the environment and agricultural productivity. Basically, the SMCRA has two main purposes: regulation of active mines and reclamation of abandoned mines (SMCRA, 1977). The regulation of an active mine is as follows:

• Standards of Performance: SMCRA sets up environmental

standards for mines to follow during their operations and

reclamation of mined lands. In doing this, problems related to

discharge of mine drainage are avoided.

• Permitting: SMCRA requires that mining companies obtain

authorization before using the land and they must provide a

detailed proposal of mining activity and land reclamation

program after mining.

• Bonding: SMCRA requires that mining companies post a bond

that will cover the cost of reclamation after mining. The bond is

not released until reclamation is fully accomplished.

• Inspection and Enforcement: SMCRA enforces the inspection of

mining operations and punish companies that violate any of the

statute.

SMCRA has created an endowment funds for the cleaning up of mine lands abandoned before the passage of the statute in 1977 and also respond to emergencies such as landslides, land subsidence, and fires and to carry out high priority cleanups in states without approved

33 programs. States with approved programs can also use AML funds to pay for programs to insure homeowners against land subsidence caused by underground mining. This act resulted in the creation of the Office of Surface Mining (OSM) within the Department of Interior (SMCRA,

1977).

One flaw of the SMCRA act is that it varies from state to state so each individual State has a regulatory program depending on the nature of the vegetation, climate, geology, soil, mining and reclamation technique but the basic goal is always the protection of the environment and human health (SMCRA, 1977).

1.3.4 Ohio legislation

Strip mining began in Ohio in 1914 but was accelerated by the high demand for coal during the Second World War. This resulted in the compromise of the quality of the environment (Dickman, 1964).

In 1948, the first strip mine law called, “the Strip Coal Mine Act” was enacted to control the activities of mining operators and reclaimed mined lands. In the reclamation program, mined lands are leveled and revegetated with grasses, shrubs or trees. The law mandated mine operators to have state-issued license and also pay a bond of $100 per acre for reclamation. The strip mine law was amended in 1949 and 1981 to make it more compliant with the Federal law (Dickman, 1964).

1.4 Biological Indicators

Stream contamination caused by inorganic chemical species can affect the biological components of the streams. The biological components measured in the stream include IBI (Index of Biotic Integrity), ICI

(Invertebrate Community Index) and PIBI (Periphyton Index Biotic

Integrity). Each of the biological indicators is characterized by different metrics. A metric is defined as a characteristic of the biota that changes in some predictable way with increased human influence

(Karr et al., 1986). These metrics enable the researcher to predict the nature of the changes at that site.

1.4.1 Index of Biotic Integrity

The index of biological integrity (IBI) is developed to assess the condition of water bodies by direct evaluation of biological attributes

(Karr et al., 1986). The IBI is a composite index that integrates structural, ecological, trophic, and reproductive attributes of fish assemblages at multiple levels of organization (Karr et al., 1986). The

IBI is modified to suit different ecoregions and to assess the condition of fish assemblages in first–order to fourth–order streams. The IBI score is used to measure the population and diversity of fish species in a particular area.

1.4.2 Invertebrate Community Index

The Invertebrate Community Index (ICI) is a tool used to monitor and assess the activities of free-flowing rivers and streams. This is based on the determination of the macroinvertebrate communities within a stream. Macroinvertebrate studies are important to assess the population of tolerant or intolerant insect taxa and also indicate the general water quality of the area (Sunday Creek Watershed Group,

2003). Aquatic invertebrate has been used for many years to assess the pollution of flowing water (DeShon, 1995). The ICI metrics included total number of mayfly taxa, percent of tribe, percent of tolerant organisms and total number of EPT taxa.

1.4.3 Periphyton Index of Biotic Integrity (PIBI)

PIBI is one of the biological indices used for assessing water quality, but it is not widely used (Stevenson and Lowe, 1986; and Stevenson and

Pan, 1999) because of the use of IBI and ICI by biologist. PIBI is calculated based on taxonomic and non-taxonomic features. The taxonomic features include relative taxa richness and indicator species while the non-taxonomic features include biomass and chlorophyll per unit area (Stevenson and Pan, 1999). The PIBI was calculated by the biologists of the STAR research team.

CHAPTER TWO --- STUDY AREA

2.0 Site Description

The study area is located within the Western Allegheny Plateau (WAP)

Ecoregion in the southeastern part of Ohio (Figure 2-1) and deals almost exclusively with the Shade River watershed, which is a tributary of the

Figure 2-1 Location of the study area in Ohio.

Ohio River. The Shade River watershed has a drainage area of 572

square kilometers (221 square miles) and it is found within the Shade

River Basin (Childress and Jones, 1983). It is located on the boundary between the lower part of Athens County, and the upper and eastern part

of Meigs County (Figure 2-2). The Shade River Basin is characterized by

eastward dipping strata dissected by steep and narrow valleys.

Figure 2-2 Location of the Shade River Watershed and its surrounding sub- watersheds.

The watershed is divided into the West, Middle and East branches. This

research is focused on the West and the Middle branches (Figure 2-3), which are adjacent to each other. These two branches were not

extensively sampled prior to this study.

Figure 2-3 Map showing the West and Middle branches of the Shade River

Watershed.

2. 1 Climate

The WAP area has a warm to temperate rainy climate. The climate is influenced by tropical maritime moisture-laden air masses, which moves

39 generally northeast from the Gulf of Mexico (Cross and Hedges, 1959).

Meigs County has cold winters, but intermittent thaws generally preclude a long lasting snow cover (Gilmore and Bottrell, 1999). The average temperature during the winter is 32o F (0o C). Summer is normally humid

and hot with an average temperature of about 76o F (26o C). The highest

temperature is recorded in July while the lowest is recorded in January.

The mean annual temperature of the area is about 55o F (12.8o C).

According to the rainfall records of Ohio, the mean annual precipitation is about 1036 millimeters (41 inches) with 660 millimeters

(26 inches) going back into the atmosphere as a result of evapotranspiration. The surface runoff is about 376 millimeters (15 inches), which is discharged into streams. The annual groundwater recharge rate is about 101.6mm (4 inches). The precipitation recorded in the study area is two inches greater than that of the whole Ohio State.

The highest amount of precipitation is normally recorded in July with an average value of 125 mm while the lowest is in February with a value of

60 mm. The annual snowfall in the area ranges from 88 mm (3.5 inches)

to over 825 mm (33 inches), of which most occur from January through

March. The average seasonal snowfall is about 525 mm (21 inches)

(Gilmore and Bottrell, 1999).

The average relative humidity during mid–afternoon is about 60%

but at dawn, the average humidity is about 80% (Gilmore and Bottrell,

1999). During summer, there is 60% of sunshine throughout the day while 35% sunshine is experienced during winter.

2.2 Topography

The topography of the area is moderately hilly with wide but flat valleys

(Cross and Hedges, 1959) separated by narrow ridgetops. Elevation of the area varies from 700 to 1200 feet above sea level. Most of the study area lies in the unglaciated dissected plateau of southeastern Ohio, which consists of sand and gravel deposited as outwash from glacier with some marshy parts.

2.3 Geology

The WAP ecoregion is made up of sedimentary rocks that were deposited during the Pennsylvanian to the Permian System. The Shade River Basin is underlain by the Conemaugh and Monongahela Formations of the

Pennsylvanian System and the Dunkard Group of the Permian System

(Gilmore and Bottrell, 1999). The Conemaugh is exposed in western part of Meigs County; the Dunkard and Monongahela Formations are found in the central part of Meigs County; and Dunkard Formation of the Permian system is found in the eastern part of the Meigs County (Brant and

DeLong, 1960).

Table 2-1 General Stratigraphy of the rocks in the Hocking Basin (Cross and

Hedges, 1959).

System or Series Group or Formation Character of material Clay, silt, sand, and gravel Recent deposited on flood plains of stream Till composed chiefly of clay with few thin lenses or beds of sand and gravel Pleistocene of limited areal extent. Interbedded and inter lensing sand gravel deposited as outwash by

Quaternary glacial melt waters. Massive to thin-bedded sandstone, varicolored Permian Dunkard shales with small amount of limestone, underclay and coal Shale, sandstone, redbeds, Monongahela limestones, underclays, minable coal and shale in repetitive cyclical sequences. Sandstone, sandy shales, Conemaugh underclays, few thin coal seams, conglomerate and limestone in repetitive cyclical sequences. Coals, underclays, Alleghany limestones with small amount of shales, sandstone, flints, iron ores in repetitive cyclical sequences. Conglomerate, sandstone, Pottsville shale, coals, underclays with smaller amount of flints, limestone, ironstones in repetitive

Pennsylvanian cyclical sequences. Logan, Cuyahoga, Conglomerate, sandstone, Mississippian Sunbury, Berea, siltstone, shale Bedford Devonian Ohio Thick shale

These Formations consist of sandstone, siltstone, limestone, shale and coal with some minor amount of conglomerate. The coal producing seams within the basin including the Lower Kittaning, Upper Freeport,

Pittsburgh, Pomeroy and Meigs Creek (Brant and DeLong, 1960). The bedrock within the basin is basically sandstone and shale with some less exposed limestone strata. Most of bedrock areas have a northeast- southwest strike (Sturgeon et al., 1958) with a calculated average dip of the area is 41.1 feet per mile toward the southeast.

The sediments of Pennsylvanian System were deposited from 320

to 298 Ma, and are divided into the Monongahela, Conemaugh,

Allegheny and Pottsville formations.

The Monongahela Series consists of limestone, sandstone, shale,

siltstone and coal. It is thicker than 350 feet and can be distinguished by

laterally extensive, non-marine limestone layers.

The Conemaugh Series consists of sandstone, siltstone, shale,

mudstone with minor amounts of coal and limestone. This formation

ranges from 350 to 490 feet in thickness and it is characterized by the

rapid horizontal and vertical lithological changes. This formation has

color ranging from gray, green, red, and brown to black with multi –

colored mudstones, and thin to thick marine shale with limestone in the

lower two-thirds of the unit (Cross and Hedges, 1959).

Figure 2-4. Map of Ohio showing the geology of the WAP ecoregion

(After Brant, 1964).

The Allegheny and Pottsville Series ranges from Lower to Middle

Pennsylvanian in age. Both series are considered as one unit because of their similar characteristics and lithologies but the Pottsville is Lower

Pennsylvanian in age. Both series consist of interbedded sandstone, siltstone, claystone, shale, conglomerate and coal. The Allegheny Series varies from 450 to 620 feet in thickness and has high amount of economically viable coal and clay. The thickness of the Pottsville varies from 60 feet in the northeast and increases to 440 feet in the southeast.

2.4 Soils

Soils in Ohio were formed in a humid, temperate climate under deciduous forest vegetation (Conrey et al., 1934). The soils are divided into six major categories based on parent material, topography and drainage, color of the surface soil, color and character of the surface, and reaction (neutral or acid) of the surface soil.

In the WAP, there are five different soil groups, namely: Gilpin–

Upshur – Lowell – Guernsey Association; Coshocton – Westmoreland –

Berks Association; Clermont – Rossmoyne – Avonbury – Cincinnati

Association; Shelocta – Brownsville – Latham – Steinsbury Association; and Westmoreland – Homewood – Loudonville Association (shown in

Figure 2-5). The most common Association is the Gilpin – Upshur –

Lowell – Guernsey while the least Association is the Clermont –

Rossmoyne – Avonbury – Cincinnati Association. The soils in the WAP

45 are associated with acidic sandstone, shale and limestone. The soils are moderately deep and low in fertility and organic matter. The principal soils in the WAP ecoregion are well drained light colored soils developed in residual sandstone, siltstone and shale. These soils are very good for the agricultural practices. Most of the terrace and alluvial soils in the valleys are thicker, more productive, acidic, well drained and moderately permeable.

The Shade River Basin is characterized by soil associations including Gilpin – Rarden – Aaron and Upshur – Gilpin Soil

Associations. These are well drained soils found on ridge tops and recent alluvium and lacustrine sediments, which are typical of floodplain topography (Gilmore and Bottrell, 1999). Upshur – Gilpin Association makes up of about 67% of Meigs County and it is moderately deep, strongly sloping to very steep, well-drained soil derived from siltstone, sandstone, and shale (Gilmore and Bottrell, 1999). Gilpin – Rarden –

Aaron Association is made up of about 7% of the county and it is also characterized by moderately deep to deep, strongly sloping to steep, well-drained and moderately well-drained soils derived from siltstone, sandstone, and shale. This soil has moderate permeability (Gilmore and

Bottrell, 1999).

Figure 2-5 Map of Ohio showing the different Soil Associations (Assessed at www.dnr.state.oh.us/.../images/SoilRegions.gif).

2.5 Land use and land cover

Land use is strongly influenced by topography and the availability of mineral resources (Friel et. al., 1987). The WAP Ecoregion covers about 84,500 km2 . Of this area, 72% is forested, while agriculture

constitutes 23% of the total area (Sayler, 2006). The remaining 5% is

made of urban built-up, non-forested wetland, small water bodies and

barren areas. In Athens and Meigs Counties, Forest makes up 66% of

the land use while agriculture and urban development make up 26 and

4.8% respectively (Figure 2-6). The rest is covered by non-forested

wetland, small water bodies and barren areas.

The forest area is a mixed mesophytic forest (consists of diverse

composition of trees) dominated by mixed oak and mixed temperate

trees. Hardwood, small strands of pine, and other evergreen trees also

form part of the forest.

Agriculture is a major economic activity in Athens and Meigs

Counties and it is one of the major land uses in these counties. In 1987,

these counties had 528 farms, which included about 85,076 acres

(Gilmore and Bottrell, 1999). Among the agricultural activities include

general farming of pasture, hay, corn, soybean, and animal rearing.

Most of the agricultural activities occur in valleys within the rural

settings in these counties.

Other land use activities include residential development and

barren areas. These encompass surface mines, gravel pits, quarries and

48 transitional areas (Friel et. al., 1987). Abandoned underground and surface mines are the source of the acid mine drainage problems within the Ecoregion.

Figure 2-6 Land use and land cover within Athens and Meigs counties (Source of data was from ESRI).

2.6 WAP Groundwater Hydrology

The WAP region is made of different basins drained by dendritic networks of streams. These streams are recharged by surface runoff and groundwater outflow. The area has been extensively dissected by drainageways (Gilmore and Bottrell, 1999). The drainage pattern of the streams in the WAP are dendritic with a network of streams such as Long

Run, Big Run, Pratt Fork, Kingsbury Creek, Meigs Creek, Sugar Run,

Little Scioto, Queer Creek, Elkhorn Creek, Raccoon Creek, Bear Creek and Cat Run (Figure 2-6). The drainage systems in Meigs County drain into the Ohio River by the way of the Shade River (Figure 2-3), Leading

Creek, Raccoon Creek, and small direct drainageways (Gilmore and

Bottrell, 1999).

The sandstone, siltstone, limestone and coal in the bedrock are productive aquifers. These aquifers occur as discontinuous lenses of sand and gravel interbedded with fine material and, in some places, as perched aquifers of limited lateral extent. Valleys formed within the

Appalachian Plateau have a network of fracture systems (Wyrick and

Borchers, 1981) responsible for the vertical infiltration of groundwater along valley walls. Most of the sandstones within this region are compact and well cemented with low hydraulic conductivity, but secondary fractures increases their permeability.

Figure 2-7 Drainage map of the various creeks within the WAP ecoregion showing the main stems of the Shade River Watershed.

CHAPTER THREE --- BACKGROUND

3.0 Introduction

Numerous studies have documented the contaminations of stream water and sediments by ion concentrations (e.g., Monday Creek in

Ohio). In some cases, the contamination is mostly caused by the advective and dispersive movement of heavy metals due to mining activities. Some writers (Amaning, 2006; Pond, 2004; Robson and Neal,

1997; Lehane et al., 2004) have studied the effect of factors such as bedrock geology, soil types, climate, land use, and urbanization on the chemistry of water and sediments collected within streams in different parts of the world.

3.1 Bedrock Geology

The geology of a particular locality determines the ionic composition of the streamwater and sediments and also influence the pH and hardness of surface waters. Surface waters are normally acidic when the concentrations of strong acid anions, such as nitrates, sulfates or chlorides, exceed the concentrations of base cations delivered from watersheds (Henriksen et al., 1992). Areas dominated by carbonate rocks (limestone, dolomite and marble) have high buffering capacity

(Lehane et al., 2004). Waters drained from these areas are characterized by high pH that neutralizes the effect of acid rain or acid mine drainage. According to the results of Amaning (2006), the streams and

52 sediments in the WAP are characterized by high calcium and magnesium concentrations with relatively high alkalinity values. Some exceptions occur for sites that are probably contaminated with AMD.

In areas characterized by silica-rich rocks such as sandstone, siltstone, quartzite or granite, the rocks are very resistant to weathering and have low buffering capacity (Lehane et al., 2004). In the silica–rich terrane, the rate of neutralization is slow as compared to the rate of acid production. In some areas within the WAP, the rocks have high iron and sulfur content, which result in the problem of AMD. Although there are limestone lithologies within some of these areas, the rate of acid production exceeds the rate of neutralization so the problem persists.

3.2 Soil Types and Sediments

Soils in the study area were mostly formed from the weathering of bedrock and they affect water quality physically, chemically, and biologically. Carbonate terrane is characterized by carbonate–rich soils which act as buffering agents for acidic precipitates. These soils act as alkaline medium in lime dosing processes, where the alkaline soil is poured in the channel of running acidic water. Physically, soils act as a sieve for the filtration of solid impurities to enhance the quality of water.

Sediments on the other hand are very important indicators of stream health. The addition of fine–grained sediments change the structure of aquatic communities, diminish productivity, reduce the permeability of the benthic materials used by fish for spawning

(Drewes, 1984), decrease the amount of dissolved oxygen (DO), and increase water turbidity. Most of the sediments, normally in the form of clasts, clays, organic matter, oxides and hydroxide of certain elements, are deposited in streams and rivers as a result of stream bank and upland erosion. The finer sediments, by the virtue of their surface charges, sorption rate, and large surface area are capable of sorbing large amount of the contaminants and, therefore act as a reservoir for the accumulation of both biotoxic and non-biotoxic substances (Wang,

2001). The effects of siltation on aquatic life are devastating in the ecoregions of Ohio where: (1) erosion and runoff are moderate to high,

(2) clayey silts that attach to and fill the interstices of coarse substrates are predominant, and (3) streams and rivers lack the ability to expel sediments from low flow channels which results in a longer retention time and greater deposition of silt in the low flow channels (Rankin et al., 1996).

3.3 Climate

Climatic changes have the tendency to alter water quality significantly by changing temperature, flows, runoff rate and timing,

54 and the ability of watershed to assimilate waste and pollutants (Gleick and Adams, 2000). Changes in temperature can affect the activities of micro-organisms in the soil and aquatic environments. It can also lead to increased toxicity of metals and bioaccumulation within organisms. High temperatures reduce the concentration of dissolved oxygen within aquatic environments, increasing microbiological activities and in some cases, increasing mortality rate.

Wet climatic conditions result in floods or high runoff rates, carrying sediments and other impurities into the streams and creating instabilities within aquatic environments. However, the concentrations of the contaminants or trace elements are diluted. Conversely, during periods of prolonged drought conditions, there is an increase in microbiological activities and algae growth as a result of stagnation.

Under this condition, contaminant concentrations or trace elements concentrations increase due to the high rate of evaporation. The high evaporation rate affects biological activity rate and oxygen saturation in the stream.

3.4 Land Use

Land use is a major problem affecting the chemistry of streams in

Ohio. As discussed in Chapter 1, agriculture and mining are the causes of most of the environmental related problems in Ohio. Mining of coal has resulted in the deforestation of large acres of land, AMD, land

55 subsidence and erosion. Surveys across the Shade River Watershed

Basin indicate that most of the land in the headwaters of the basin are marked by disturbed land, high walls, and spoil piles devoid of vegetation as a result of erosion (Childress and Jones, 1983).

Agriculture has created many problems for aquatic environments.

It has increased the concentrations of nutrients and decreased the amount of dissolved oxygen within the aquatic environment.

Agriculture, through deforestation (burning of biomass) releases carbon and other elements stored in the biomass (Rodriguez et al., 2004).

These elements undergo oxidation in the atmosphere resulting in the formation of acid rain or dangerous gases, such as carbon dioxide that results in the formation of greenhouse gases.

In forested areas devoid of any influence from human activities, vegetative cover determines the amount of nutrient or organic matter available for the soil and it also acts as a medium for preventing erosion, that is, by reducing rainfall impact. In this case, most of the rain soaks into the soil rather than running off the ground.

Mining alters the chemistry of nearby aquatic environments

(Pond, 2004). During and after mining, coal-bearing strata are removed and accumulated into spoil piles. These spoils are erosion prone and they lack nutrients to support vegetation. Runoff from spoil piles carries sediments and contaminants into streams.

3.5 Urbanization or Anthropogenic Input

In developed areas covered by pavement and buildings, there is little infiltration of water into the soil, thereby causing high runoff, and stream flow with high peaks. This normally results in high flooding frequency and a decrease in base flow and groundwater recharge.

Stream and river surveys in Ohio during the 1970s and 1980s revealed that most of the streams were contaminated with untreated municipal and industrial wastewater (Rankin et al., 1996). The untreated waste increased the nutrient content of the streams and reduced the DO, causing algae blooms. Most streams with algae blooms had reduction in the population of fish and other aquatic organisms.

The presence of algae affects the quality of the water in terms of the nutrients and the chemical variables. The presence, abundance, diversity, and distribution of aquatic species in surface water are dependent upon myriad of physical and chemical factors or variables such as temperature, suspended solids, pH, nutrients, riparian habitats,

DO, total dissolved solids (TDS), acidity, electric conductivity (E.C.), and alkalinity (Wang, 2001).

3.6 Summary of the Chemistry of Phase I (2005 data)

Amaning (2006) studied the WAP ecoregion on a regional scale in

Phase 1 of the STAR project. He studied the effects of geology and land characterization on streams and streambed sediments chemistry, and

their effects on aquatic organisms within fifty reference sites (sites

with low impact from anthropogenic activities). He concluded that

10000 EVAPORATION/ CRYSTALLIZATION

1000

L) / WEATHERING 100

TDS (mg

10 PRECIPITATION

1 0 0.2 0.4 0.6 0.8 1 Na+/(Na++Ca2+)

Figure 3-1 Gibbs diagram for the 2006 summer data.

rock weathering is the dominant control on the water chemistry. His

Na + conclusion was based on a plot of TDS against on a Gibb’s ( + +CaNa 2+ )

diagram (Figure 3.1), in which the stream water fell within the portion

of the diagram dominated by rock weathering. His studies showed that the waters were composed mainly of calcium and bicarbonate with

limestone being the dominant carbonate rock. The presence of

limestone produced alkalinity that buffered the pH of the waters.

The dissolution process of calcite was still incomplete. The dissolution of calcite or carbonate rocks and the hydrolysis of silicate minerals were the main processes that consumed the hydrogen ions. The pH measured was neutral to alkaline, which was good for natural waters. He stated that the general healthy status of the reference streams could be attributed to low anthropogenic sources and the presence of limestone lithologies. Almost all of the chemical parameters fell within the USEPA criteria for the protection of aquatic life except DO, phosphate and manganese. He further stated that the low DO measured at some sites was due to the temperature variation and the low or no flow condition during the summer of

2005. The high manganese concentrations could probably be attributed to the areas affected by mining activities and the high phosphate concentration was due to agricultural activities. The high iron concentration in the sediments was probably due to the local geology (shale, coal and iron ore) of the WAP ecoregion. The iron concentration resulted in the formation of AMD in some area characterized by mining activities. Waters and sediments in areas with coal geology are characterized by AMD. The chemical indicators of

AMD in streams include low pH (<6), low alkalinity (<20 mg/L), iron

(>0.5 mg/L), manganese (> 0.5 mg/L), sulfate (> 75 mg/L), aluminum

(> 0.3 mg/L), specific conductivity (> 800 µS/cm), and zinc (> 5 mg/L)

(FWPCA, 1968; USEPA, 1986).

Amaning (2006) examined the relationship between the water chemistry, geomorphic and biological components of the stream and concluded that there was no significant correlation between the ionic concentrations and the biological indicators. He did find that there was a significant correlation between water chemistry and organic matter, as well as between sediment chemistry and organic matter.

Amaning (2006) concluded, based on the relationship between water chemistry and land use that land use may not be a strong predictor of water chemistry at the reference sites but there was a significant correlation between nitrate and urban land use. This suggested an impact from other anthropogenic activities since there was no correlation between nitrate and agricultural land use.

CHAPTER FOUR--- METHODOLOGY

4.0 Methodology

Field work for this project was done during the summer from 5th

July to 17th August 2006, for fish, macroinvertebrate, algae, habitats, water chemistry, and hydrology. Data collected in a previous thesis

(Amaning, 2006) during the first phase of this project in the summer of

2005 was also used in the analysis of the results. The present study is restricted to the streamwater and streambed sediment chemistry and field parameters of the project.

4.1 Selection of Sampling Points

Fifty sites were selected for summer 2005 and forty-three sites for summer 2006. The selection was based on a Geographic Information

System (G.I.S.) data generated for reference sites according to the

USEPA criteria. The sites were designed in such a way that they were spatially distributed (Figure 4-1).

Out of the ninety-three selected sites, twenty-two concentrated within the Shade River Watershed (Figure 4-2) while the rest of the sampling sites were scattered within the thirty-six counties making up the WAP ecoregion as shown in Figure 4-1.

Five of the sites were re-sampled to check whether there is an analytical variation in the physical and chemical compositions of the

(WAP)

Figure 4-1 Map showing the ninety– three sites sampled in the WAP during summer 2005 and 2006.

streams. The five reference sites were randomly re–selected from the sites sampled in 2005 to measure the influence of the 2005 drought conditions on the reference assemblages, which excluded small streams and impaired sites that were sampled in 2006. The site selection in

2005 was restricted to exclude very small streams (less than 10 square miles) of catchment area and impaired sites.

Figure 4-2 Sampled sites within the West and Middle branches of the Shade River, summer 2006

The sampling sites in 2006 were chosen from watersheds that represented variations in the habitat and geomorphic conditions so that their influence on biological assemblages could be examined. Sampling sites with moderate to extensive available biological, chemical and habitat data were selected so that there would be a broad stressor gradient to allow the testing of the classification tool that would be developed later and would consider geomorphology, water chemistry,

63 nutrient supply, and sediment gradient. Due to this factor, watersheds or sampling points dominated mainly by AMD impacts rather than other stressor gradients and their influence on the biological assemblages were not considered.

Sites with historical data from USEPA within the WAP ecoregion were randomly selected, based on GIS data generated, so that the present data could be compared to the historical data. The pool of sites was restricted to sites with fish and macroinvertebrate data and historical water chemistry data. This was the other reason why highly impacted AMD sites were not considered. The selection was stratified to obtain equivalent number of sites from four quartiles of drainage size and subecoregion. Collection of the 2006 summer data was designed to help verify whether biological conditions were similar to historical data and to provide a biological gradient along to examine patterns in macroinvertebrates, fish and algal communities.

4.2 Field Parameters

Chemical and physical parameters measured in the field included pH, dissolved oxygen (DO), electrical conductivity (EC), temperature, salinity, total dissolved solids (TDS), acidity and alkalinity, and discharge (measured by the hydrologists of the STAR research team).

Three different readings were taken and averaged to minimize the effect of large error values. Salinity was useful in calibrating the DO meter.

Temperature and pH were measured using a calibrated YSI 60 pH meter. The meter was calibrated using buffer solutions of pH 7, 4 and

10 consecutively.

DO was measured using a calibrated YSI 55 DO meter.

Calibration depended on the stream water salinity and the altitude of the sampling.

Electrical conductivity, salinity, and TDS were measured using

CO150 model HACH Conductivity meter. These parameters were measured by inserting the electrode of the meter into the stream after calibrating the meter with conductivity standard solution of 1409µS/cm.

Conductivity and TDS are directly proportional. Field parameters were measured after the electrode had stabilized in the streamwater to ensure an accurate temperature and to minimize the effect of large errors.

Alkalinity and acidity were the only field parameters that were determined in the field using titration. Alkalinity was used in determining the concentrations of bicarbonates within the water samples.

Table 4.1 Field parameters and their units of measurement Parameter Measuring tool Unit pH YSI 60 pH meter None DO YSI 55 DO meter mg/L

Acidity or Alkalinity HACH Digital Titrator mg of CaCO3 /L Electric Conductivity Conductivity meter µS/cm Temperature YSI 60 pH meter o C Total Dissolved Solids Conductivity meter mg/L

Alkalinity of a solution is the ability of the solution to buffer

against drop in pH (Delbeek and Sprung, 2005) or the acid neutralizing

potential of the stream. Higher alkalinity affords greater ability to

prevent rapid change in pH. The concentration of alkalinity is

influenced by the presence of anions such as carbonates, bicarbonates,

borates, and hydroxides (Delbeek and Sprung, 2005).

The alkalinity of the streamwater was determined in the field by titration using filtered water samples, HACH digital titrator, sulfuric

acid digital titrator cartridge (0.16N), and bromcresol green-methyl red

powder pillow. Titration was done by collecting 25 milliliters of the

filtered water sample into 250 milliliters Erlenmeyer flask. The

contents of one indicator powder pillow was added to the water sample

and swirled to mix uniformly. Sulfuric acid was added in drops until

the color of the solution changes from green to pale red or light pink at

the endpoint of titration (HACH, 2005). The alkalinity was calculated

by:

D N 50mg Alkalinity = ( 1 ) * ( ) * ( of CaCO3 ) D 2 V meq

D 1 is the number of counts from the digital titrator cartridge.

D 2 is the total number of counts in the digital titrator per millimeter of

solution, which is equivalent to 800 counts.

N is the normality of the solution in the digital titrator cartridge

(0.1600n or 1.600N)*1000mL (meq).

V is the volume of the water sample used in titrating (0.025 L)

Acidity, on the other hand, is the base neutralizing potential of

the stream. The acidity of the stream water was determined in the field

by titration using filtered water samples, HACH digital titrator, sodium

hydroxide (0.01600N) digital titrator cartridge and a phenolphthalein

powder pillow. Titration was done by collecting 25 milliliters of the

filtered water sample into 250 milliliters Erlenmeyer flask. The

contents of one indicator powder pillow was added to the water sample

and swirled to mix uniformly. Sodium hydroxide was added in drops

until the color of the solution changes from colorless light pink at the

endpoint of titration (HACH, 2005). The equation for the calculation of

the acidity is similar to that of the alkalinity.

4.3 Streambed Sediment Samples for Cations Analyses

The sediments were sampled using a WILDCO stainless steel sampler

(equipment shown in Appendix B, Figure B.2) at each of the sites. The

equipment was rinsed with diluted 2% nitric acid (HNO3 ) and washed

67 with distilled water before it was forced into the streambed at a depth of about 130 mm (five inches). The core was wrapped with a plastic film, placed in a transparent polythene bag, and then transferred into a sample bag that has an air tight seal. The sample bag was placed in an ice–chest at a temperature of 4o C (Pepper et al., 1996) in the field and

was later transferred into a fridge prior to future analyses.

Sediment samples were collected because sediments are porous

solids with long resident times and high sorption capacities for

containments (Pepper et al., 1996). Samples were taken from areas with

higher amount of fine material because contaminants are preferentially

attached to fine particles. Fine particles have high sorption rate and

large surface area as compared to coarse rock particles.

4.4 Streamwater Samples for Cations and Anions Analyses

Pollutants move faster in water than in sediment so water samples were taken at places with significant amount of flow. Flowing water bodies

were sampled at the center of the stream because water flows faster and

higher in the center of the channel than the edges (Pepper et al., 1996).

Six water samples were collected at each site and placed into a

high density polypropylene sample bottles. Four of the samples were

placed into 250 milliliter bottles and the other two placed into a 125

milliliter bottles. These sampling bottles were used because they

prevented the sorption, precipitation or change of form of water

68 samples while in storage (Pepper et al., 1996). All sampling bottles were washed with 2% by volume HNO3 and then rinsed twice with the

filtered water sample prior use. The six samples were divided into three

filtered and three unfiltered samples. Both filtered and unfiltered

samples were collected for cations and anions analyses.

4.4.1 Filtered Samples

These samples were collected directly from the stream and filtered

through 0.45µm millipore filter membrane. This was done to remove the

suspended materials and algae. The algae and some of the suspended

materials in the sample feed on some of the ions under investigation, and also clog the nebulizer of the inductively coupled plasma (I.C.P)

emission spectrometer. Filtration was done by using vacuum filtration

(equipment shown in Appendix B, Figure B.1).

The vacuum filtration method involved the use of both suction

and gravity to draw liquid from a funnel through the filter membrane into a filtering flask attached to a vacuum pump. After the filter holder assembly was placed on the filtering flask, the filter membrane was dampened with deionized water to ensure adhesion to the holder and the vacuum pump used to create suction (HACH, 2005). This process drew water from the funnel into the filtering flask, after that the funnel was filled with the stream water. The first few millimeters of filtered water samples were used to rinse the flask and the sampling bottles.

After filtering, two of the water samples were kept in a 250 milliliter sampling bottles for cations and anions analyses while the other sample was kept in a 125 milliliter bottle for ammonia and phosphate analyses. Samples for cation analyses were preserved by adding 20% by volume HNO3 (1 milliliter of HNO3 per every 100

milliliter of the sample) to prevent the formation of metal complexes,

which could affect the outcome of the chemical analyses. Samples for

the anion analyses were not preserved because of the reactivity of the

anions. The samples for ammonia and phosphate analyses were treated

with 20% by volume sulfuric acid (H2 SO4 ). One 1 milliliter of sulfuric

acid was added to every 100 milliliter of water sample. This was also

done to prevent the formation of ammonium and phosphate complexes.

4.4.2 Unfiltered Samples

These samples were collected directly from the stream into the bottle

after rinsing the bottle with some of the unfiltered water sample. The

purpose for collecting unfiltered sample was to determine the chemistry

of the suspended matter or total ion concentration of the stream water.

The same number of samples was collected for the unfiltered samples

using the same methods of preservation. The difference between the

filtered and unfiltered sample composition is the presence of suspended

matter in the unfiltered samples.

After sampling, details of the project and samples were recorded on a duct tape label using an indelible marker pen and adhered onto the sample bottles and bags. The duct tape was covered with another transparent tape to ensure that the labels were legible and also, not easily erased.

4.5 Laboratory Work

The laboratory work involved chemical analysis of the water and sediment samples. Sediment and the samples for the anions analyses were analyzed immediately after sampling because of the tendency of the anions degrading easily.

Water sample for the cations analyses were not performed immediately because of the number of ions to be determined. The samples were stored in a refrigerator, ensuring that the specimens did not change chemical form and thus yield false negative results (Pepper et al., 1996).

4.5.1 Sediment Samples Analyses

The sediments were analyzed to determine the organic content and the cations present, because sediments have high adsorption capacity for cations. Acid digestion method 3050B was used to obtain the leachate and determine the concentrations of the trace elements and

71 the cations (USEPA, 1996) while loss on ignition (LOI) was used to determine the organic content.

4.5.1.1 Sediment Organic Matter Determination

LOI is a dry combustion experiment used to determine the amount of organic matter within sediment samples. In this method, 5 to 10 grams of the sediment was transferred into a crucible, weighed and placed in an electric drying oven at a temperature of 105o C for 6 hours.

It was allowed to cooled, reweighed, and reheated in a muffle furnace at a temperature of 600o C for twenty hours again (Goldin, 1987). The

samples were then placed in a desiccator and reweighed at room

temperature. The difference between the initial and final weight of the

sample was the total organic content of the sample (Soil and Plant

Council, 1992). The organic content was determined by the formula:

− ( 105 ww 600 ) * 100 w600

o Where W105 is the weight of the sediment sample heated at 105 C,

o while W600 is weight of the sample heated at 105 C.

4.5.1.2 Sediment Cation Determination

In this method, the sediment sample was digested using the acid digestion method according to the USEPA Method 3050B. This method

72 included the determination of dissolved metals and total recoverable metals in the leachate. Five grams of the sample was dried in an oven for about 6 hours, allowed to cool and sieved to remove the pebbles and impurities in the sample. An amount of 0.5 gram of the sieved sample was placed in a test tube and mixed thoroughly with 5 milliliters of 1:1 concentrated HNO3 to form a mixture. This mixture was heated in a

digester at a temperature of 98o C for 15 minutes without boiling to

form a digestate, which was allowed to cool. An amount of 2.5

milliliters of concentrated HNO3 (1:1 HNO3 ) was added to the digestate

again and refluxed for 30 minutes. The mixture was heated again till

the volume reduced to about 3 milliliters and then allowed to cool.

After this, 1 milliliter of distilled water and 1.5 milliliters of 30%

hydrogen peroxide (H2 O 2 ) was added to the mixture in the tube. More

of the 30% H2 O 2 was added to the digestate until it produced no

effervescence but the total amount of H2 O 2 added did not exceed 5

milliliters. The mixture was heated till the volume reduced to about 3

milliliters. It was allowed to cool and diluted with distilled water to 50

milliliters. This was stirred and filtered through Whatman No. 41 filter

paper (USEPA, 1996). The filtered digested sample was used for cation

analysis using the Inductively Coupled Plasma Emission Spectrometer.

4.5.2 Water Samples Analyses

Analysis of the water samples involved the use of spectrophotometric methods for both cations and anions. Anions except the chlorides and bicarbonates were determined using a HACH Spectrophotometer while the cations were determined using both an Inductively Coupled Plasma

Emission Spectrometer and an Atomic Absorption Spectrophotometer.

The cations analyzed included iron (Fe), aluminum (Al), magnesium

(Mg2+), calcium (Ca2+), sodium (Na+ ), lead (Pb2+), potassium (K+ ),

nickel (Ni2+), cobalt (Co2+), zinc (Zn2+), cadmium (Cd2+), and

2+ 3- chromium (Cr ) while the anions included total phosphates (PO4 ),

- - - chlorides (Cl ), nitrates (NO3 ), bicarbonates (HCO3 ), and sulfates

2- (SO4 ). Silica (SiO2 ) and ammonia (NH3 ) were the only compounds investigated.

4.5.2.1 Cations

Water samples were digested for the total recoverable or dissolved metals prior to the cation analysis according to the USEPA method

3005A. In this method, a test tube with 25 milliliters of the sample was placed in the digester. An amount of 2.5 milliliters of concentrated 1:1

HNO3 and hydrochloric acid (HCl) were added to the sample. The

mixture was heated till the volume reduced to about 3 milliliters. The

mixture was allowed to cool, stirred, and filtered through Whatman No.

41 filter paper to remove the impurities (USEPA, 1996). The filtered

74 sample was diluted to 50 milliliters for cation analysis using the

Inductively Coupled Plasma Optical Emission Spectroscopy. Potassium was also determined later using the atomic absorption spectrophotometer.

4.5.2.2 Anions

All the anions, except chloride and bicarbonates were analyzed using the HACH spectrophotometer and the standards for the various anions in the geochemical laboratory of the Geological Sciences

Department of Ohio University, while the cations were analyzed using

ICP equipment in Ohio University chemistry department. Before the analyses, the concentrations obtained for the various ions were calibrated using different standardized solutions to plot a graph for correction or limiting the errors.

4.5.2.2.1 Nitrate

Nitrate concentration was determined using the EPA approved method number 8192 called Cadmium Reduction Method (HACH,

2005). This involved the addition of nitraVer6 reagent powder pillow into 15 milliliters of the sample in a cell (analytical bottle). The sample was shook and allowed to undergo a reaction time of two minutes.

NitriVer3 was also added to 10 milliliters of the 15 milliliters sample,

75 and allowed to undergo a reaction time of three minutes. The equations for the chemical reactions are:

- + - 2+ NO3 (aq) + Cd + 2H (aq) NO2 (aq) + Cd (aq) + H2 O (l)

- + + NO2 (aq) + sufanillic acid (aq) 2H (aq) Diazonium Salt(s) + 2H2 O(l)

The sample was finally allowed to undergo a ten minute reaction time.

The content of the solution in the cell was placed in the cell holder of

the spectrophotometer. The spectrophotometer was first zeroed by using

a blank solution (HACH, 2005) before the analysis.

4.5.2.2.2 Sulfate

Sulfate concentration was determined using the EPA approved

method number 8051 called the Turbidimetric or SulfaVer4 method

(HACH, 2005). In this method, SulfaVer4 reagent powder pillow was

added to 10 milliliters of the water sample. The reagent contained

barium chloride and the sulfate content of the solution was determined

by its quantitative precipitation with barium chloride (HACH, 2005).

The reaction produced barium sulfate colloids that increased the

turbidity of the solution. This turbidity was proportional to the

concentration of sulfate in the solution. The chemical reaction is

represented by:

2+ 2- Ba (aq) + SO4 (aq) BaSO4 (s)

The mixture was poured in the cell of the spectrophotometer and

allowed to undergo a reaction time of five minutes after shaking it. The

76 mixture was placed in the equipment for analysis after it had been zeroed using a blank solution.

4.5.2.2.3 Total Phosphate

Determination of the total phosphate concentration in the water sample involved the use of the Acid Digestion Method or Acid

Hydrolyzable Digestion (method 8180) and the PhosVer3 or Ascorbic

Acid Method (HACH, 2005).

The sample was first digested by adding 2.0 milliliters of 5.25 N sulfuric acid to 25 milliliters of the water sample. The mixture was boiled gently for 30 minutes and cooled. One milliliter of 5.0 N sodium hydroxide solution was added, swirled and topped to 25 milliliters again with deionized water (HACH, 2005). Ten milliliters of the digested sample is poured into a cell and one phosVer3 phosphate powder pillow was added. The mixture was inverted several times and reaction proceeded for two minutes. The mixture was poured into the cell for spectrophotometric analysis after zeroing the equipment with blank solution.

Acid digestion converted the inorganic phosphate into orthophosphate, which also reacted with molybdate to form molybdate complex. This is represented by the equation:

- - 12MoO3 (s) + H2 PO4 (aq) (H2 PMo12O 40) (aq)

The complex is reduced by the ascorbic acid, giving an intense molybdenum blue color (HACH, 2005).

4.5.2.2.4 Ammonia

Ammonia concentration was determined using the EPA approved method number 8038 called Nessler Method (HACH, 2005). In this method, 25 milliliters of the sample was poured into a cell. Three drops of mineral stabilizer was added to the sample, closed with a stopper and inverted several times to mix uniformly. Three drops of polyvinyl alcohol dispersing agent and 1 milliliter of Nessler reagents were then added.

The Nessler reagent contained mercuric iodide which produced a yellow coloration due to the presence of ammonium ions in the water sample. The mineral stabilizer complexes hardness while polyvinyl alcohol dispersing agent aids the color formation in the reaction of

Nessler reagent with ammonium ions (HACH, 2005). The intensity of the yellow color produced is proportional to the concentration of the ammonium in the solution. This is determined accurately by using photometric reading.

The mixture was swirled and allowed to undergo a reaction time of two minutes. The content of the solution in the cell was placed in the cell holder of the spectrophotometer. The equipment was first zeroed by using a blank solution (HACH, 2005).

4.5.2.2.5 Chloride

Chloride concentration was determined using a Chloride

Combination Ion Selective Electrode. The electrode was cleaned with emery paper and distilled water, and filled with 10% potassium nitrate

(KNO3 ) solution. The electrode was calibrated by using standardized

chloride solutions with concentration ranging from 10 to 1000 mg/L. In

the calibration process, the electrode was placed in the lower standard

solution (10 mg/L) to stabilize before transferring it into the other

standards. Three different readings were taken and averaged.

One milliliter of 5M sodium nitrate (NaNO3 ) ionic strength adjustment (ISA) solution was added to 50 milliliters of the every water sample in a beaker to keep the ionic strength of the samples and the standards constant. The beaker was covered with paraffin to reduce the vaporization of the sample. The solution was allowed to undergo a reaction time of about 5 minutes after stirring it with the electrode. The

electrode was allowed to stabilize in the solution before taking the

measurement. Three different readings were taken and averaged to

minimize the error range of the electrode. The electrode was cleaned

with distilled water after every analyzed sample.

4.6 GIS Processing of Data

The measured concentrations of the cations, anions, and field parameters were plotted on the map of Ohio as showing in the Figures in chapter 5. This was done by using the ArcMap and ArcCatalog of the

ArcGIS Desktop software. The table of the concentrations of the ions and the field parameter in Microsoft Excel were saved as a DBF file and imported into the ArcGIS program. The latitude and longitude coordinates of the various sites were saved as tab delimited text file and displayed as XY coordinates in ArcMAP using a Geographic

Coordinate System (G.C.S.) called North America Lambert Conformal

Conic projection (GCS_North_American_1983_UTM). This projection plotted the coordinates as points on the map. The projected coordinates and the DBF files were joined together using a unique identification number called OBJECTID or FID projection.

The ninety-three sampled sites were exported onto the thirty-two

(32) counties making up the WAP ecoregion within Ohio while twenty- two (32) samples were exported and clipped onto streams located within the Shade River Watershed.

The attribute table of the DBF file was joined to the attribute table of the sampled points to form one joined table. The joined table was used in plotting the spatial distribution of the concentration of the ions and the field parameters. Using symbology of joint table’s layer

80 properties, the concentrations were classified into three classes using the Natural Breaks (Jenks) method. The classes were represented by red

(bad sites), yellow (intermediate sites) and green color (good sites).

4.7 Cation–Anion Balances (Error Calculation for the Streamwater Chemistry)

The accuracy of the chemical analyses was checked by using the formula:

( Σ Cations − Σ Anions ) Percentage difference = 100* (Σ Cations Σ+ Anions )

The quantity of cations does not equal the quantity of anions measured

for the summer 2006 data. The sources of error may probably be due to

missing analysis of major dissolved species, samples containing

particulates that dissolved into solution during analysis, minerals

precipitate out of solution during analysis (Deutsch, 1997) or due to

mechanical error in the digital titrator during alkalinity titration.

According to Amaning (2006), the calculated average analytical

error associated with the summer 2006 data (site 44 to 93) is 4%. From the analysis, only two samples had values exceeding 6% (that is, sites

80 and 92).

CHAPTER FIVE---RESULTS

5.0 Results

In this chapter the correlation analysis and descriptive statistics

(spatial distribution) of the chemistry of the WAP ecoregion and the

Shade River watershed are presented. The results are represented graphically in GIS plots with different colors. The red colors indicate bad sites, yellow indicate intermediate and green represent good sites.

5.1 Streamwater Chemistry

The water chemistry included the field parameters and the ions obtained from the analysis of the filtered streamwater and streambed sediment samples (shown in Tables 5-1 to 5–8; Figures 5-1 to 5-46; Appendix A,

Figure A.1. to A.11.) within the WAP and the Shade River watershed.

5.1.1 Field parameters

The field parameters measured included temperature, pH, alkalinity, acidity, electric conductivity, total dissolved solids and dissolved oxygen.

5.1.1.1 pH Changes in pH can indicate change in the level of pollution of a stream and can cause alterations in the structure and function of the ecosystem. pH affects the solubility of minerals and trace metals in streamwater.

Low pH accelerates the release of metals from rocks or sediments. pH values measured in the WAP ranged from 6.2 at site 6 to 8.2 at sites 12,

13 and 25 (Figure 5-1). The calculated mean pH was 7.5 and the standard deviation was 0.5.

The pH within the western and middle branches of Shade River

Watershed ranged from 6.9 to 8.2 with sites 34 and 25 having the lowest and the highest values respectively (Figure 5-2). The calculated mean pH was 7.6 and the standard deviation was 0.3. The pH criteria for the protection of aquatic life set by the US Environmental Protection Agency

(EPA) range from 6.5 to 8.5.

These results show that all sites within the middle and western branches of the Shade River Watershed fall within the EPA criteria for the protection of aquatic life. However, in the WAP ecoregion, site 6 presented pH lower than 6.5.

Note: The USEPA criteria for pH for the protection of aquatic life ranges from 6.5 to 8.5

Figure 5-1 Spatial distribution of the measured pH within the WAP ecoregion

Figure 5-2 Spatial distribution of the measured pH within the Shade River Watershed

5.1.1.2 Temperature

Temperature exerts a major influence on the biological activity and growth of aquatic organism, that is, the higher the temperature, the greater the biological activity. The rate of chemical reaction within an aquatic system depends on the temperature of the system. The temperature of the stream depended on the time sampling was done.

The temperature measured within the WAP ecoregion ranged from

18.2 o C at site 52 to 30.8 o C at site 19; with a mean temperature of 23.6

o C and a standard deviation of 2.7.

Within the Shade River Watershed, the temperature ranged from

19.5 o C at site 38 to 25.2 o C at site 23; with a mean temperature of 22.8

o C and a standard deviation of 1.3.

5.1.1.3 Dissolved Oxygen (DO)

Dissolved oxygen is one of the important indicators of water quality.

High oxygen concentration can affect the survival of fish while low

concentration can result in mortality. Fluctuation in the temperature of

the stream can affect the concentration of dissolved oxygen in the

stream. The higher the temperature, the lower the amount of dissolved

oxygen.

The measured DO in the WAP ranged from 2 mg/L at sites 6 and

59, to 15 mg/L at site 17 (Figure 5-3); with a mean of 6.3 and a

85 standard deviation of 2.4. The USEPA lower limit criterion of DO concentration for aquatic life is 4.0 mg/L (USEPA, 1986).

The concentration of DO in the Shade River Watershed ranged from 3 to 13 mg/L (Figure 5-4). Site 33 had the lowest value (3 mg/L) while STAR site 26 had the highest value (13 mg/L). The average concentration for the dissolved oxygen calculated was 5.7 mg/L and the standard deviation was 2.8.

Note: The USEPA criteria for DO for the protection of aquatic life is greater 4 mg/L

Figure 5-3 Spatial distribution of the measured DO within the streams in the WAP ecoregion

Figure 5-4 Spatial distribution of the measured DO within the Shade River Watershed

5.1.1.4 Total Dissolved Solids (TDS)

TDS are made up of the inorganic chemical species or ions in the stream water. The main contributing species to the dissolved solids include nitrate, sulfate, carbonates, bicarbonates, phosphates, chloride, calcium, potassium, magnesium, sodium, and iron.

In the WAP, the TDS ranged from 71 mg/L at site 53 to 3375 at site 12 (Figure 5-5); with a mean value of 294 mg/L and a standard deviation of 385. Sites 12 and 14 had values beyond the USEPA criteria for drinking water (Figure 5-5) but site 15 had value beyond the USEPA criteria for both drinking water and aquatic life.

The concentration of the total dissolved solids in the Shade River

Watershed ranged from 158 mg/L at site 35 to 276 mg/L at site 39

(Figure 5-6); with a mean concentration of 209 mg/L and a standard deviation of 37. All the sites had TDS concentrations within the USEPA range for drinking water quality (750 mg/L) and that for the protection of aquatic life (1500 mg/L).

Note: The USEPA criteria for TDS for the protection of aquatic life is 1500 mg/L

Figure 5-5 Spatial distribution of the measured TDS within the WAP ecoregion

NB: TDS values measured within the Shade River fell within the USEPA criteria but red, yellow and green colors were used to indicate areas of low, lower and lowest concentrations respectively.

Figure 5-6 Spatial distribution of the measured TDS within the Shade River Watershed

5.1.1.5 Electric Conductivity

The electric conductivity deals with the mobility of the charged chemical species in the water sample. High electric conductivity is measured in area with high TDS while lower values are measured at site with high dilution or dissolution rate.

The WAP had electric conductivity (EC) ranging from 150 µS/cm at site 68 to 6370 at site 12 (Figure 5-7); with a mean concentration and a standard deviation of 579 µS/cm and 723 respectively.

The measured EC in the Shade River Watershed ranged from 311 to 543 microsiemens per centimeter (µS/cm) as shown on Table 5-1 and

Figure 5-8. The average and standard deviation for the EC calculated were 419 µS/cm and 72 respectively. The highest concentration was measured at STAR site 35 while the lowest value was measured at site

39, just like that of the TDS. All of the sites had EC lower than the

USEPA maximum concentration for drainage basin water quality criteria for non-drinking and drinking water (750 mg/L).

Note: The USEPA criteria for DO for the protection of aquatic life is 750 mg/L

Figure 5-7 Spatial distribution of the measured EC within the WAP ecoregion

NB: EC values measured within the Shade River fell within the USEPA criteria but red, yellow and green colors were used to indicate areas of low, lower and lowest concentrations respectively.

Figure 5-8 Spatial distribution of the measured EC within the Shade River Watershed

5.1.1.6 Alkalinity

Alkalinity is very important to the water quality because it prevents the

fluctuation in the pH. It is the sum of the total components in the water

that tend to elevate the pH of the water above a value of about 4.5

(USEPA, 1986) and it neutralizes the acid in the water. Alkalinity in

streamwater is normally increased by ions including bicarbonates,

carbonates, hydroxides, and phosphates.

Alkalinity concentration in the WAP ranged from 19 mg of

CaCO3 /L at site 8 to 314 mg of CaCO3 /L at site 14 (Figure 5-12); with a

mean concentration of 131 mg of CaCO3 /L and a standard deviation of

55. The entire sites had values within the USEPA criteria for aquatic

life except site 8.

For the 2006 data, a problem was detected for the measured

alkalinities. Alkalinity values correlated inversely with the ion balance,

suggesting high error in the alkalinity measurements. The problem is

that the alkalinity measurements in the 2006 were done with a HACH

digital titrator but in 2005, alkalinity measurement was done using a

burette in the laboratory. It should be noted that the 2006 alkalinity

values were significantly lower than those of 2005, regardless of a

higher maximum value for the pH. For this reason, the alkalinity values

for the 2006 were rejected.

5.1.1.7 Acidity

Acidity is the capacity of water to neutralize a base by means of chemical buffering.

The concentration of acidity within the WAP ecoregion ranged from 5 mg CaCO3/L to 220 mg CaCO3/L (Figure 5-9). The lowest concentration was measured at site 40 while the highest was at site 81.

A mean concentration of 34 mg CaCO3/L and a standard deviation of 29 were calculated.

The acidity in the Shade River Watershed ranged from 5 mg

CaCO3/L at site 40 to 39 mg of CaCO3 /L at site 22 (Figure 5-10); with

a mean concentration of 22 mg of CaCO3 /L and a standard deviation of

Figure 5-9 Spatial distribution of the measured acidity within the WAP ecoregion

Figure 5-10 Spatial distribution of the measured acidity within the Shade River Watershed

5.1.2 Anions

The anions measured included nitrate, sulfate, total phosphate and chloride. Apart from chloride, all the anions measured were classified as nutrients.

5.1.2.1 Nitrate

The nitrate measured is in the form of nitrogen, which is an essential nutrient for aquatic life. Source of nitrate in the stream include runoff from agricultural lands and anthropogenic sources such as domestic wastes. High concentration of nitrates and other nutrients in streams result in a process called eutrophication (high algae growth on the surface of water bodies).

Within WAP, the nitrate concentration ranged from 0.02 mg/L at site 3 to 12 mg/L at site 13 (Figure 5-11); with a mean concentration and a standard deviation of 0.46 mg/L and 1.50 respectively. Sites 5, 9,

12, 13, 20, 44, 56, 71, 72, 74, 78, 81, 83, 84, 90 and 92 had values beyond the USEPA criteria for aquatic life (Figure 5-11).

The concentration of nitrate within the Shade River Watershed ranged from 0.03 mg/L at site 41 to 0.31 mg/L at site 30 (Figure 5-12): with a mean concentration of 0.12 mg/L and a standard deviation of

0.07. The measured nitrate concentration fell within the USEPA criterion for the protection of aquatic life (0.35 mg/L).

Note: The USEPA criteria for nitrate for the protection of aquatic life is 0.34 mg/L

Figure 5-11 Spatial distribution of the measured nitrate concentration within the WAP ecoregion

NB: Nitrate concentration within the Shade River fell within the USEPA criteria but red, yellow and green colors were used to indicate areas of low, lower and lowest concentrations respectively.

Figure 5-12 Spatial distribution of the measured nitrate within the Shade River Watershed

5.1.2.2 Sulfate

The concentration of sulfate in the WAP ecoregion ranged from 4 mg/L at sites 29, 30 and 43 to 2233 mg/L at site 10; with a mean concentration of 129 mg/L and a standard concentration of 392.

Within the Shade River Watershed, the concentration of sulfate ranged from 4 to 29 mg/L (Figure 5-13). The highest concentration was measured at site 35 while the lowest was measured at sites 29, 30 and

43. The average concentration for sulfate in the Shade River was 13 mg/L and the calculated standard deviation was 7.

The USEPA criterion for sulfate concentration for the protection of aquatic life is 860 mg/L (USEPA, 1986), while that for drinking water is 250 mg/L. The concentration of sulfate within the WAP ecoregion fell within the USEPA criteria for aquatic life except sites 9,

10, 14 and 15 as shown in Figure 5-14 but within the Shade River, all the sites had sulfate concentrations within the USEPA criteria.

Note: The USEPA criteria for sulfate for the protection of aquatic life is 860 mg/L

Figure 5-13 Spatial distribution of the measured sulfate concentration within the WAP ecoregion

NB: Sulfate concentration within the Shade River fell within the USEPA criteria but red, yellow and green colors were used to indicate areas of low, lower and lowest values respectively.

Figure 5-14 Spatial distribution of the measured sulfate concentration in the Shade River Watershed

5.1.2.3 Total Phosphate

Phosphate, just like nitrate is important for aquatic plant growth. Both phosphate and nitrate are derived from a variety of natural and artificial sources, including rock erosion, decomposition of organic materials, man-made fertilizers, and sewage.

Total phosphate concentration within the WAP ranged from 0.01 mg/L (at sites 51, 54, 58 and 93) to 0.93 mg/L (at site 13) (Figure 5-

15); with an average concentration of 0.20 mg/L and a standard deviation of 0.20.

Within the Shade River Watershed, total phosphate concentration varied from 0.17 mg/L at site 41 to 0.55 mg/L at site 36 (Figure 5-16); with a mean and standard deviation of 0.30 mg/L and 0.10 respectively.

The concentration of the total phosphate in the water samples was greater than the USEPA criterion of 0.05 mg/L and this can interfere with coagulation in water treatment plants (USEPA, 1986).

Most of the sites had values beyond the USEPA criteria for the protection of aquatic life (0.05 mg/L) as shown in Figure 5-15, except sites 53, 56, 57, 68, 78 and 83 which had values below detection level.

All the sites in the Shade River Watershed had values beyond the criteria for the protection of aquatic life (Figure 5-16). The high total phosphate concentration might be due to high concentration of orthophosphate, metaphosphate or organic rich phosphate and this could result in algae bloom or eutrophication.

Note: The USEPA criteria for total phosphate for the protection of aquatic life is 0.05 mg/L

Figure 5-15 Spatial distribution for total phosphate concentration within the WAP ecoregion

NB: Total phosphate concentration within the Shade River were above the USEPA criteria but red, yellow and green colors were used to indicate areas of extremely high, very high and high concentrations respectively.

Figure 5-16 Spatial distribution of the measured total phosphate concentration in the Shade River Watershed

100

5.1.2.4 Chloride

Chloride is one of the conservative ions in streamwater. The concentration of chloride was relatively low in the Shade River and the

WAP ecoregion. Often, chloride concentrations reflect input from roads during winter. Chloride concentration within the WAP, ranged from 2 mg/L at site 38 to 178 mg/L at site 13 (Figure 5-17); with a mean concentration of 20 mg/L and a standard deviation of 27.

The concentration of chloride within the Shade River ranged from

2 mg/L at site 38 to 20 mg/L at site 41 (Figure 5-18); with a mean concentration of 8 mg/L and a standard deviation of 4.

The measured chloride concentration for both the WAP and Shade

River were within the USEPA criteria for the protection of aquatic life

(860 mg/L) and that for drinking water (250 mg/L).

101

Note: The USEPA criteria for chloride for the protection of aquatic life is 860 mg/L

Figure 5-17 Spatial distribution of the measured chloride concentration in the WAP ecoregion

Figure 5-18 Spatial distribution of the measured chloride concentration in the Shade River Watershed

102

5.1.3 Streamwater cations

The cations measured in the water samples were divided into major cations and the trace elements.

5.1.3.1 Major cations

The major cations were the positive dissolved ions species in water with concentrations greater than 1.0 mg/L. This included sodium, potassium, calcium and magnesium.

5.1.3.1.1 Sodium

The concentration of sodium in the WAP ranged from 5 mg/L at site 54 to 427 mg/L at site 14 (Figure 5-19). The calculated mean concentration and standard deviation were 50 mg/L and 62 respectively.

Within the Shade River, the concentration of sodium ranged from

18 to 115 mg/L (Figure 5-20). The highest concentration was measured at site 32 while the lowest concentration was measured at site 25. The mean concentration calculated was 80 mg/L with a standard deviation of 28.

103

Figure 5-19 Spatial distribution of the measured sodium concentration in the WAP ecoregion

Figure 5-20 Spatial distribution of the measured sodium concentration in the Shade River Watershed

104

5.1.3.1.2 Potassium

The concentration of potassium within the WAP varied from 2 mg/L at sites 45, 47, 48, 49, 52, 53, 54, 55, 59, 60, 64, 68, 91 and 93 to

9 mg/L at sites 1, 2, and 27 (Figure 5-21); with a mean of 5 mg/L and a standard deviation of 2.

Within the western and middle branches of Shade River

Watershed, the concentration of potassium varied from 6 to 9 mg/L

(Figure 5-22). The highest concentration was measured at site 27. The mean concentration and the standard deviation calculated were 7 mg/L and 1 respectively.

105

Figure 5-21 Spatial distribution of the measured potassium concentration within the WAP ecoregion

Figure 5-22 Spatial distribution of the measured potassium concentration in the Shade River Watershed

106

5.1.3.1.3 Calcium

The concentration of calcium within the WAP ecoregion was also high ranging from 16 to 240 mg/L (Figure 5-23). The highest concentration was measured at site 15 while the lowest concentration was measured at site 73. The mean concentration calculated was 84 mg/L with a standard deviation of 48.

The concentration of calcium was quite high within the Shade

River Watershed ranging from 84 to 131 mg/L (Figure 5-24). The highest concentration was measured at site 42 while the lowest concentration was measured at site 28. The mean concentration calculated was 106 mg/L with a standard deviation of 13.

107

Figure 5-23 Spatial distribution of the measured calcium concentration within the WAP ecoregion

Figure 5-24 Spatial distribution of the measured calcium concentration in the Shade River Watershed

108

5.1.3.1.4 Magnesium

The concentration of magnesium within the WAP varied from 4.0 mg/L at site 73 and 88 to 243 mg/L at site 10 (Figure 5-25); with a mean concentration of 27 mg/L and a standard deviation of 38.

Within the Shade River, the concentration of magnesium varied from 17 to 32 mg/L (Figure 5-26). The highest concentration was measured at site 39 while the lowest concentration was measured at site

35. The mean concentration and the standard deviation calculated were

25 mg/L and 4 respectively.

109

Figure 5-25 Spatial distribution of the measured magnesium concentration in the WAP ecoregion

Figure 5-26 Spatial distribution of the measured magnesium concentration in the Shade River Watershed

110

5.1.3.2 Trace Elements

These were elements that occurred in usually small concentration (< 1 mg/L) in water sample. Trace metals were sorbed more onto finer particles than in water. The trace elements measured included iron, manganese, aluminum, barium, cadmium, cobalt, chromium, copper, lithium, nickel, lead, strontium and zinc).

5.1.3.2.1 Iron

The concentration of iron in the WAP varied from 0.02 mg/L at sites 56 and 87 to 6.30 at site 26 (Figure 5-27); with a mean and standard deviation of 0.38 mg/L and 0.98 respectively. Site 9, 26 and

71 had concentration greater than 1.0 mg/L, the USEPA criterion for the protection of aquatic life (shown in Figure 5-27).

The iron concentration measured within the Shade River

Watershed ranged from 0.03 to 6.30 mg/L. The highest concentration was measured at site 26 while the lowest concentration was measured at sites 25 and 42. The mean concentration and the standard deviation calculated were 0.41 mg/L and 1.31 respectively. Site 26 was the only site (shown in Figure 5-28) that had concentration greater than the

USEPA criteria for freshwater aquatic life (1.0 mg/L).

111

Note: The USEPA criteria for iron for the protection of aquatic life is 1.00 mg/L

Figure 5-27 Spatial distribution of the measured iron concentration in the WAP ecoregion

Figure 5-28 Spatial distribution of the measured iron concentration in the Shade River Watershed

112

5.1.3.2.2 Manganese

The concentration of manganese in the WAP varied from 0.11 mg/L at sites 38 and 39 to 5.89 mg/L at site 10 (Figure 5-29); with a mean and standard deviation of 0.49 mg/L and 0.74 respectively.

The concentration of manganese was relatively high as compared to the USEPA criterion for the protection of aquatic life (0.1 mg/L).

Manganese within the Shade River ranged from 0.11 mg/L at sites 38 and 39 to 0.47 mg/L at site 42 (Figure 5-30); with a mean of 0.22 mg/L and a standard deviation of 0.11.

The manganese concentration of iron within the WAP and the

Shade River Watershed were beyond the USEPA criterion for the protection of aquatic life.

113

Note: The USEPA criteria for manganese for the protection of aquatic life is 0.10 mg/L

NB: Iron concentrations within the WAP were above the USEPA criteria but red, yellow and green colors were used to indicate areas of extremely high, very high and high concentrations

Figure 5-29 Spatial distribution of the measured manganese concentration within the WAP ecoregion

NB: Iron concentrations within the Shade River were above the USEPA criteria but red, yellow and green colors were used to indicate areas of extremely high, very high and high concentrations respectively.

Figure 5-30 Spatial distribution of the measured manganese concentration within the Shade River Watershed

114

5.1.3.2.3 Aluminum

Aluminum is the most abundant element in the earth’s crust, and the third most common element (Sparling and Lowe, 1996). It is one of the elements that determines the impact of acid mine drainage (AMD) in stream water.

The concentration of aluminum within the WAP ranged from 0.10 mg/L at sites 44 and 45 to 0.49 mg/L at site 27 (Figure 5-31): with a mean concentration of 0.21 mg/L and a standard deviation of 0.07

The concentration of aluminum measured within the Shade River

Watershed ranged from 0.15 mg/L at site 40 to 0.49 mg/L at site 27

(Figure 5-32); with a mean concentration of 0.23 mg/L and a standard deviation of 0.08. All the sites within the WAP and Shade River

Watershed had aluminum concentration within the USEPA standard

(0.50 mg/L) for the survival of aquatic life.

115

Note: The USEPA criteria for aluminum for the protection of aquatic life is 0.5 mg/L

Figure 5-31 Spatial distribution of the measured aluminum concentration within the WAP ecoregion

Figure 5-32 Spatial distribution of the measured aluminum concentration within the Shade River Watershed

116

5.1.3.2.4 Other Elements

Elements such as barium, strontium, silica and ammonia in the water samples collected with the WAP and Shade River were also analyzed.

The statistical descriptions of these elements are found in Appendix A,

Figures A.1. to A.4.

5.2 Streambed Sediment Chemistry

Cations were the only ions analyzed from the sediment sample because of their sorption capacity and their positive charges. The elements analyzed included the major cations (sodium, potassium, magnesium and calcium,) and the trace elements (iron, manganese, aluminum, beryllium, lithium, cobalt, chromium, copper, molybdenum, nickel, lead, strontium and zinc).

5.2.1 Sodium

Sodium concentration within the sediments in the WAP ranged from 329 mg/Kg at site 54 to 1833 mg/Kg at site 43 (Figure 5-33); with a mean concentration of 724 mg/Kg and a standard deviation of 291.

The concentration of sodium in the sediments within the Shade

River Watershed ranged from 456 mg/Kg at site 23 to 1833 mg/Kg at site 43 (Figure 5-34); with a mean concentration of 997 mg/Kg and a standard deviation of 290.

117

5.2.2 Potassium

The concentration of potassium in the WAP sediments ranged from 533 mg/Kg at site 88 to 13110 mg/Kg at site 6 (Figure 5-35); with a mean concentration of 2283 mg/Kg and a standard deviation of 1754.

The sediment concentration of potassium within Shade River

Watershed ranged from 1001mg/Kg at site 22 to 7337 mg/Kg at site 40

(Figure 5-36); with a mean concentration of 2983 mg/Kg and a standard deviation of 1614.

5.2.3 Magnesium

The sediment concentration of magnesium taken within the WAP ranged from 369 mg/Kg at site 83 to 16023 mg/Kg at site 35 (Figure 5-

37); with a mean concentration of 3601 mg/Kg and a standard deviation of 2518.

The concentration of magnesium in the sediment taken within the

Shade River Watershed ranged from 2536 mg/Kg at site 22 to 16023 mg/Kg at site 35 (Figure 5-38); with a mean concentration of 4738 mg/Kg and a standard deviation of 2809.

5.2.4 Calcium

The concentration of calcium in the sediments for the WAP ranged from 1035 mg/Kg at site 81 to 73853 mg/Kg at site 79 (Figure 5-

118

39); with a mean concentration of 7278 mg/Kg and a standard deviation of 11915.

The sediment calcium concentration in the Shade River

Watershed ranged from 4409 mg/Kg at site 33 to 23372 mg/Kg at site

35 (Figure 5-40); with a mean concentration of 6644 mg/Kg and a standard deviation of 4389.

5.2.5 Iron

The sediment concentration of iron measured within the WAP ranged from 9098 mg/Kg at site 34 to 76461 mg/Kg at site 74 (Figure 5-

41); with a mean concentration of 26996.3 mg/Kg and a standard deviation of 12974.1.

The concentration of iron within sediments in the Shade River

Watershed ranged from 9098 mg/Kg at site 34 to 49468 mg/Kg at site

24 (Figure 5-42); with a mean concentration of 23991 mg/Kg and a standard deviation of 13013.

5.2.6 Manganese

The sediment concentration of manganese measured within the

WAP ranged from 130 mg/Kg at site 54 to 2399 mg/Kg at site 30

(Figure 5-43); with a mean concentration of 740 mg/Kg and a standard deviation of 449.

119

The sediment concentration of manganese within sediments taken from the Shade River Watershed ranged from 370 mg/Kg at site 28 to

2399 mg/Kg at site 30 (Figure 5-44); with a mean concentration of 958 mg/Kg and a standard deviation of 590.

5.2.7 Aluminum

The concentration of aluminum measured within the WAP sediments ranged from 2760 mg/Kg at site 9 to 44895 mg/Kg at site 64

(Figure 5-45); with a mean concentration of 15451 mg/Kg and a standard deviation of 9495.

The aluminum concentration of the sediment taken within the

Shade River Watershed ranged from 3366 mg/Kg at site 35 to 20495 mg/Kg at site 43 (Figure 5-46); with a mean concentration of 9385 mg/Kg and a standard deviation of 4707.

5.2.8 Other Elements

Elements such as lithium, cobalt, chromium, copper, nickel, strontium, and zinc in the sediment samples were also analyzed. The statistical descriptions of these elements are found in Appendix A, Figure A.5. to

A.11.

120

5.3 Total Organic Carbon (TOC)

The TOC calculated for streambed sediments within the WAP ranged from 0.1% at sites 17, 20 and 32 to 7.9% at site 56; with a calculated mean of 2.3% and a standard deviation of 2.2.

TOC calculated for the streambed sediments in the Shade River

Watershed ranged from 0.1% at site 32 to 1.4% at site 22; with a mean concentration of 0.3% and a standard deviation of 0.3.

5.4 Stream Discharge Rate (Flow)

Flow measurements were taken with wadable pygmy meter at area with significant amount of flow within the streams. Flow measurement of summer 2006 were measured and compiled by Mr. William Carson while that for summer 2007 was done by Mr. Shannon Cook.

The discharge rate within the WAP varied from 0.0035 cfs at site

52 to 123.13 cfs at site 13. The calculated mean and the standard deviation are 4.80 cfs and 18.53 respectively. Eighteen sites had no or low flow.

The discharge rate within the Shade River Watershed ranged from

0.08 cfs (ft3 /s) at site 35 to 4.67 cfs at site 23; with a mean discharge rate of 0.64 cfs and a standard deviation of 1.02. Sites 32, 38 and 41 had low or no flow so the streams were not gauged.

121

Figure 5-33 Spatial distribution of the measured sodium concentration in sediments within the WAP ecoregion

Figure 5-34 Spatial distribution of the measured sodium concentration in sediments within the Shade River Watershed

122

Figure 5-35 Spatial distribution of the measured potassium concentration in sediments within the WAP ecoregion

Figure 5-36 Spatial distribution of the measured potassium concentration in sediments within the Shade River Watershed

123

Figure 5-37 Spatial distribution of the measured magnesium concentration in sediments within the WAP ecoregion

Figure 5-38 Spatial distribution of the measured magnesium concentration in sediments within the Shade River Watershed

124

Figure 5-39 Spatial distribution of the measured calcium concentration in sediments within the WAP ecoregion

Figure 5-40 Spatial distribution of the measured calcium concentration in sediments within the Shade River Watershed

125

Figure 5-41 Spatial distribution of the measured iron concentration in sediments within the WAP ecoregion

Figure 5-42 Spatial distribution of the measured iron concentration within sediments in the Shade River Watershed

126

Figure 5-43 Spatial distribution of the measured manganese concentration in sediments within the WAP ecoregion

Figure 5-44 Spatial distribution of the measured manganese concentration in sediments within the Shade River Watershed

127

Figure 5-45 Spatial distribution of the measured aluminum concentration in sediments within the WAP ecoregion

Figure 5-46 Spatial distribution of the measured aluminum concentration in sediments within the Shade River Watershed.

128

Table 5 – 1 Physical and field parameters measured in the WAP ecoregion (Summer 2005 and 2006).

Site TDS EC OEPA No. Number Latitude Longitude Temp (oC) pH (mg/L) (µS/cm) DO (mg/L) S01300 3.501997 1 39.45778 -82.20056 21.5 6.7 316 609 3 S01340 0.901995 2 39.54780 -82.28190 19.7 6.4 347 640 3 S06322 0.202000 3 39.62278 -81.35556 22.3 7.5 449 934 4 S06500 2.301996 4 40.01670 -80.77310 26.2 8.1 442 915 7 S06900 29.101996 5 40.47830 -80.91360 20.2 7.8 215 451 7 S09500 108.901995 6 39.35220 -82.39170 19.1 6.2 283 518 2 S09530 8.501995 7 39.21670 -82.40470 20.0 7.1 376 657 7 S09575 0.201995 8 39.38030 -82.39830 20.5 7.2 217 418 3 S17101 0.301997 9 40.58694 -81.37083 20.8 6.6 604 1241 5 S17403 0.201998 10 40.58667 -81.50972 21.0 6.3 926 1881 8 S17413 0.301998 11 40.54472 -81.69361 26.9 8.0 449 940 8 S17414 1.701998 12 40.50028 -81.61444 28.5 8.2 3375 6370 7 S17460 6.701998 13 40.71860 -81.34560 22.4 8.2 609 1253 6 S17870 6.201999 14 39.86080 -81.63750 21.9 6.8 1463 2770 3 S17879 0.201999 15 39.84780 -81.67140 24.8 7.9 1000 2020 7 S17890 0.801999 16 39.89580 -81.54810 27.7 7.6 210 475 4 S02545 2.202005 17 39.29750 -83.16595 24.0 7.6 260 544 15 S02800 8.002005 18 39.04586 -83.12741 27.0 7.2 144 304 9 S06420 2.202005 19 39.47404 -81.24243 30.8 7.9 152 319 8 S06440 0.902005 20 39.63205 -81.05585 28.6 7.5 131 276 7 S17960 32.002005 21 40.23831 -82.25080 23.8 7.5 163 336 8 S09630 27.302006 22 39.26630 -82.06830 21.2 7.7 230 441 4 S09600 17.002006 23 39.08737 -81.92498 25.2 7.4 158 335 5 S09630 0.202006 24 39.10389 -81.92284 22.7 7.9 255 509 5 S09630 9.102006 25 39.16705 -81.94020 24.4 8.2 238 495 13

129

Table 5 – 1 (Continued)

OEPA No. Site Latitude Longitude Temp (oC) pH TDS (mg/L) EC (µS/cm) DO (mg/L) S09630 5.902006 26 39.20634 -81.96862 21.5 7.7 250 482 5 S09633 2.902006 27 39.20031 -82.00905 22.7 7.9 225 448 4 S09633 5.702006 28 39.20800 -82.05269 23.0 7.8 227 460 10 S09630 24.102006 29 39.25207 -82.02538 22.8 7.5 220 441 4 S09630 25.902006 30 39.25295 -82.05099 23.4 7.4 207 418 4 S09634 2.402006 31 39.27881 -82.04310 23.9 8.0 245 500 3 S09641 0.402006 32 39.09914 -81.94148 22.3 7.5 180 359 5 S09644 1.102006 33 39.09749 -82.01529 23.2 7.6 163 326 3 S09643 5.502006 34 39.11315 -82.01635 22.8 6.9 164 336 5 S09648 0.102006 35 39.13135 -82.07428 22.5 7.6 158 311 5 S09643 10.402006 36 39.13124 -82.07647 24.0 7.3 212 437 4 S09643 9.002006 37 39.12622 -82.05617 23.3 7.6 170 345 5 S09647 0.102006 38 39.12980 -81.98368 19.5 7.3 183 338 6 S09646 0.202006 39 39.14703 -82.01043 22.2 7.9 276 543 9 S09640 11.602006 40 39.15989 -82.02017 24.5 7.3 190 430 4 S09640 19.002006 41 39.17699 -82.12611 21.6 7.4 267 516 4 S09640 16.602006 42 39.17111 -82.08354 21.7 7.0 207 405 6 S09645 2.502006 43 39.19614 -82.09972 22.5 7.7 171 339 12 S06368 0.102005 44 39.82889 -81.59583 25.0 7.7 184 386 8 S01206 0.402005 45 39.46639 -82.08139 20.5 6.7 160 337 3 S09670 0.602005 46 39.15420 -82.31360 28.4 8.2 169 359 9 S06447 3.402005 47 39.68026 -81.03075 24.5 6.7 86 182 4 S06427 0.402005 48 39.59194 -81.13694 24.3 7.1 156 327 5 S01131 0.502005 49 39.34440 -81.84780 24.3 8.1 bd 335 7 S09704 0.802005 50 40.01083 -81.57528 23.5 7.6 420 869 6 S06934 0.302005 51 40.53140 -80.99030 19.2 8.0 324 673 8

130

Table 5 – 1 (Continued)

OEPA No. Site Number Latitude Longitude Temp (oC) pH TDS (mg/L) EC (µS/cm) DO (mg/L) S06360 1.102005 52 39.62056 -81.41389 18.2 6.9 370 767 3 S01006 1.102005 53 39.26810 -81.83750 26.3 8.1 bd 289 8 S02643 0.152005 54 39.49720 -82.70250 24.3 8.2 125 271 9 S06444 1.702005 55 39.66639 -81.04823 23.8 7.4 71 151 7 S06408 0.102005 56 39.47389 -81.31500 22.2 7.3 362 752 5 S06441 0.902005 57 39.61972 -81.05000 24.6 6.6 269 563 3 S06321 8.202005 58 39.57889 -81.33056 30.0 7.7 191 403 9 S06416 0.102005 59 39.53861 -81.24000 22.1 7.0 190 400 2 S06013 0.802005 60 39.47111 -81.15000 21.9 7.0 160 335 4 S06915 1.002005 61 40.63560 -80.83610 24.8 7.8 187 393 7 S17308 3.502005 62 39.71780 -82.07420 20.6 7.2 141 296 4 S06504 1.402005 63 39.99310 -80.90110 21.5 8.1 326 678 7 S06431 2.702005 64 39.59750 -81.21390 22.7 7.4 201 422 7 S06910 6.202005 65 40.60190 -80.77170 27.1 7.5 245 515 8 S09007 3.302005 66 38.54860 -82.66250 26.1 7.2 142 300 8 S06440 0.902005 67 39.63167 -81.05694 28.0 7.6 177 373 8 S06420 2.202005 68 39.47530 -81.24080 26.0 7.4 317 150 6 S02545 2.202005 69 39.30056 -83.17222 26.7 8.0 235 494 8 S06931 0.502005 70 40.51310 -80.90250 26.3 7.7 190 401 8 S17973 1.802005 71 40.22610 -82.16470 20.7 7.6 142 301 7 S02625 4.402005 72 39.42560 -82.57420 24.4 7.2 bd 240 7 S09300 27.202005 73 38.92389 -82.79306 22.1 6.7 77 163 5 S02728 1.002005 74 38.77360 -83.35080 22.5 7.6 227 473 6 S17960 32.002005 75 40.23830 -82.25110 22.2 8.1 176 370 9 S02015 1.902005 76 38.96833 -83.06861 24.2 7.4 152 320 6

131

Table 5 – 1 (Continued)

Site OEPA No. Number Latitude Longitude Temp (oC) pH TDS (mg/L) EC (µS/cm) DO (mg/L) S06458 4.002005 77 39.73690 -81.10830 22.4 7.9 232 484 9 S02800 8.001997 78 39.04670 -83.12860 27.0 7.0 111 235 5 S06100 14.502005 79 39.90920 -80.92420 26.3 8.2 708 1450 10 S17044 3.502005 80 39.52060 -81.70390 23.9 7.8 172 362 5 S09300 12.602005 81 38.82420 -82.84780 28.6 7.0 90 192 5 S06700 7.102005 82 39.76750 -80.93580 24.6 7.8 205 431 8 S17960 12.402005 83 40.10810 -82.12720 21.1 7.6 146 307 7 S17310 12.302005 84 39.87920 -82.20610 22.9 8.0 221 463 7 S09100 5.802005 85 38.47860 -82.39780 25.5 7.3 243 507 7 S08200 9.002005 86 40.76560 -80.72250 24.1 8.0 302 629 7 S17502 0.602005 87 40.30000 -81.74722 18.4 7.5 199 418 7 S09310 0.602005 88 38.85750 -82.79640 30.1 7.5 100 214 9 S09630 8.102005 89 39.16080 -81.94920 22.8 7.5 174 365 5 S02611 4.702005 90 39.21140 -82.71500 25.8 7.1 97 206 5 S06351 0.102005 91 39.59972 -81.30278 21.0 7.0 190 397 3 S06327 0.802005 92 39.65583 -81.30028 21.5 7.3 232 484 5 S06427 1.102005 93 39.58417 -81.12917 20.1 7.3 170 357 6 bd ----- values below detection limit. Shade River Watershed sites starts from 22 to 43. Summer 2006 data are from site number 1 to 43 while summer 2005 starts from 44 to 93. OEPA--- Ohio Environmental Protection Agency

132

Table 5 – 2 Concentration of some chemical species measured in the filtered water samples

Site NO3 SO4 T. PO4 Alk. Acidity Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 1 0.16 30 0.29 49 18 29 73 9 76 27 0.09 0.23 0.12 2.8 0.31 0.34 0.35 bd bd 2 0.12 27 0.36 99 21 38 105 9 90 35 0.15 0.18 0.21 2.1 0.24 0.25 0.45 bd bd 3 0.02 69 0.18 117 27 11 17 4 185 59 0.05 0.59 0.24 1.4 0.28 0.13 0.66 178 752 4 0.04 49 0.24 182 21 33 177 6 186 55 0.07 0.18 0.20 2.3 0.28 0.31 1.41 126 390 5 6.00 14 0.25 97 27 29 43 3 86 20 0.16 0.17 0.17 1.2 0.21 0.22 0.36 76 bd 6 0.11 21 0.20 20 18 9 62 8 84 34 0.14 0.55 0.25 3.4 0.21 0.20 0.29 185 564 7 0.11 37 0.27 66 29 14 67 6 95 32 0.11 0.29 0.23 1.9 0.29 0.19 0.42 126 446 8 0.09 26 0.34 19 16 11 68 6 62 23 0.23 0.64 0.11 3.1 0.26 0.26 0.29 bd bd 9 0.42 1153 0.81 26 50 30 29 3 217 109 5.16 4.07 0.23 3.8 0.22 0.37 0.90 352 bd 10 0.27 2233 0.22 110 34 26 45 6 239 243 0.14 5.89 0.15 5.1 0.38 0.30 1.63 524 bd 11 0.12 43 0.25 145 30 33 38 6 151 74 0.12 0.27 0.23 0.7 0.25 0.11 0.72 109 bd 12 4.00 92 0.36 87 22 20 26 4 197 118 0.07 0.53 0.23 3.0 0.25 0.42 0.78 bd 405 13 12.00 26 0.93 207 47 178 191 5 167 41 0.11 0.16 0.18 2.8 0.26 0.26 0.39 171 bd 14 0.05 2089 0.20 314 33 6 427 3 198 137 0.13 0.12 0.18 1.4 0.27 0.31 3.57 bd bd 15 0.07 2089 0.32 216 37 8 254 6 240 226 0.09 0.14 0.21 2.4 0.20 0.18 3.52 283 bd 16 0.13 13 0.28 245 28 18 23 4 94 28 0.09 0.23 0.12 bd 0.14 0.29 0.49 bd bd 17 0.28 11 0.18 241 44 9 7 4 109 43 0.31 0.18 0.14 2.4 0.31 0.17 0.26 149 bd 18 0.13 6 0.32 103 30 21 19 4 41 26 0.23 0.25 0.14 1.4 0.26 0.31 0.18 31 bd 19 0.08 6 0.20 222 24 9 11 3 62 13 0.06 0.17 0.23 0.5 0.18 0.17 0.27 bd bd 20 5.00 9 0.24 89 13 27 22 3 42 11 0.06 0.12 0.19 0.2 0.16 0.27 0.31 bd bd 21 0.06 10 0.27 197 22 25 15 4 63 21 0.14 0.16 0.20 0.8 0.17 0.18 0.27 bd bd 22 0.11 14 0.22 186 39 14 83 6 102 22 0.09 0.16 0.28 2.1 0.18 0.22 0.43 bd bd 23 0.11 9 0.43 165 25 13 94 6 103 23 0.13 0.35 0.15 3.2 0.31 0.23 0.51 132 257 24 0.10 11 0.22 173 24 10 93 7 121 29 0.09 0.14 0.24 2.5 0.36 0.22 0.56 130 bd 25 0.06 14 0.32 162 21 5 18 7 90 21 0.03 0.14 0.21 0.6 0.19 0.15 0.45 bd bd

133

Table 5 – 2 (Continued)

Site NO3 SO4 T. PO4 Alk. Acidity Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 26 0.12 10 0.18 186 19 9 19 7 88 20 6.30 0.13 0.23 0.1 0.19 0.36 0.44 161 486 27 0.12 13 0.27 141 23 10 97 9 112 28 0.13 0.15 0.22 2.1 0.49 0.28 0.55 bd 476 28 0.07 9 0.33 163 29 8 19 8 84 18 0.08 0.15 0.21 0.8 0.20 0.16 0.44 215 511 29 0.13 4 0.21 160 29 7 99 8 118 30 0.14 0.24 0.22 2.5 0.26 0.08 0.54 48 bd 30 0.31 4 0.44 167 20 14 111 7 110 28 0.23 0.35 0.22 3.3 0.25 0.16 0.45 bd 364 31 0.08 23 0.24 143 21 5 74 7 109 29 0.07 0.12 0.19 2.0 0.19 0.14 0.43 165 634 32 0.23 11 0.29 201 20 14 115 7 98 26 0.23 0.23 0.20 4.2 0.20 0.17 0.59 189 bd 33 0.10 7 0.21 159 18 6 96 6 103 24 0.19 0.22 0.19 3.3 0.21 0.40 0.49 178 410 34 0.10 19 0.19 93 18 4 87 6 104 22 0.10 0.19 0.25 3.9 0.35 0.29 0.35 177 bd 35 0.14 29 0.43 117 20 4 61 6 88 17 0.12 0.20 0.38 3.7 0.19 0.21 0.35 112 bd 36 0.06 14 0.55 85 15 5 70 8 126 23 0.11 0.33 0.30 4.4 0.23 0.22 0.39 190 bd 37 0.28 11 0.19 160 16 8 86 6 107 23 0.15 0.26 0.19 3.5 0.17 0.19 0.38 bd 420 38 0.05 11 0.31 153 34 2 84 6 108 27 0.08 0.11 0.21 3.1 0.16 0.22 0.63 69 bd 39 0.10 11 0.25 145 29 7 69 7 116 32 0.10 0.11 0.15 2.5 0.18 0.34 0.53 bd bd 40 0.15 27 0.20 44 5 5 94 6 100 25 0.10 0.43 0.19 4.0 0.15 0.12 0.34 220 bd 41 0.03 16 0.17 180 22 20 105 8 127 29 0.13 0.19 0.16 2.8 0.23 0.16 0.87 274 bd 42 0.07 21 0.31 143 23 8 100 6 131 27 0.05 0.47 0.21 4.4 0.18 0.19 0.56 68 bd 43 0.04 4 0.30 149 17 4 85 8 100 20 0.37 0.14 0.19 3.0 0.27 0.16 0.41 bd bd 44 0.41 54 0.11 140 27 15 10 3 67 12 0.12 bd 0.13 20.2 0.10 0.10 0.06 74 109 45 0.07 65 0.15 100 27 11 15 2 44 12 bd 1.04 0.21 3.9 0.12 0.05 0.40 63 bd 46 0.06 56 0.06 140 27 10 28 3 46 12 0.44 0.31 0.21 4.0 0.36 0.18 0.35 108 163 47 0.05 25 0.06 67 13 10 7 2 28 7 0.49 0.82 0.19 3.7 0.16 0.09 0.21 164 191 48 0.03 28 0.03 147 27 14 8 2 60 9 0.27 0.21 0.15 4.0 0.15 0.17 0.31 78 283 49 0.05 41 0.13 133 20 21 9 2 59 9 bd 0.36 0.21 3.7 0.20 0.24 0.29 47 128 50 0.22 296 0.07 160 20 10 42 5 104 38 bd 1.54 0.27 3.2 0.22 0.13 0.88 112 188 51 0.10 246 0.01 140 27 10 14 3 114 30 0.20 0.56 0.10 4.0 0.19 0.19 0.51 42 85

134

Table 5 – 2 (Continued)

Site NO3 SO4 T. PO4 Alk. Acidity Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 52 0.05 296 0.04 80 27 15 11 2 110 38 bd 0.27 0.24 5.9 0.12 0.12 0.51 62 150 53 0.04 31 bd 107 20 13 8 2 49 8 bd 0.30 0.22 4.1 0.19 0.05 0.29 44 247 54 0.09 17 0.01 127 120 17 5 2 50 11 bd 0.39 0.21 5.3 0.17 0.20 0.13 75 91 55 0.09 21 0.06 47 20 13 8 2 21 5 bd 0.32 0.21 3.3 0.16 0.19 0.18 116 247 56 0.58 324 bd 73 27 13 47 4 109 23 0.02 0.39 0.24 4.9 0.16 0.19 0.80 111 31 57 0.07 25 bd 87 20 142 56 4 68 12 bd 0.31 0.33 3.0 0.14 0.11 0.55 97 58 58 0.06 54 0.01 107 147 51 14 3 68 9 bd 0.45 0.20 3.5 0.13 0.14 0.33 115 238 59 0.04 56 0.04 160 33 20 7 2 84 10 bd 0.37 0.25 4.1 0.12 0.08 0.33 102 107 60 0.04 25 0.05 140 27 10 9 2 57 9 bd 0.47 0.25 4.0 0.17 0.07 0.30 119 152 61 0.09 95 0.05 120 20 26 14 3 66 15 bd 0.32 0.18 4.5 0.15 0.06 0.40 103 205 62 0.30 83 0.16 147 27 11 14 5 57 10 0.22 0.38 0.20 2.1 0.31 0.20 0.25 85 126 63 0.03 95 0.07 233 47 28 91 3 64 12 0.07 0.32 0.13 4.5 0.11 0.04 0.72 83 134 64 0.22 23 0.09 167 40 13 26 2 52 10 0.04 0.72 0.22 5.3 0.14 0.04 0.44 91 128 65 0.22 138 0.18 100 27 17 40 4 61 15 bd 0.32 0.19 3.7 0.13 0.22 0.44 106 67 66 0.22 65 0.09 107 27 10 18 4 39 10 0.47 1.66 0.18 5.2 0.20 0.08 0.21 56 236 67 0.03 24 0.09 93 33 30 30 3 31 9 0.25 0.40 0.21 2.6 0.14 0.06 0.34 8 162 68 0.03 23 bd 120 40 11 10 2 45 9 0.35 0.38 0.25 5.0 0.15 0.16 0.35 151 127 69 0.10 48 0.20 233 100 18 6 3 70 35 0.31 0.36 0.21 6.0 0.15 0.11 0.24 91 95 70 0.26 83 0.07 113 27 10 18 4 43 12 0.78 0.98 0.10 3.1 0.13 0.13 0.24 126 179 71 0.35 24 0.13 80 27 39 27 4 31 9 1.02 0.86 0.26 3.9 0.16 0.12 0.23 93 208 72 0.48 37 0.13 67 20 10 15 3 23 7 0.84 0.75 0.20 5.6 0.17 0.35 0.14 77 61 73 0.26 12 0.17 53 27 14 12 5 16 4 0.65 0.98 0.23 3.7 0.20 0.10 0.15 51 161 74 0.96 49 0.24 187 100 10 8 5 64 21 0.57 0.60 0.27 5.8 0.22 0.14 0.17 88 31 75 0.22 24 0.09 140 27 11 20 5 44 9 0.33 0.56 0.19 4.5 0.14 0.31 0.23 159 279 76 0.06 94 0.55 60 27 10 18 5 35 12 0.35 0.63 0.26 3.7 0.20 0.09 0.21 90 76

135

Table 5 – 2 (Continued)

Site NO3 SO4 T. PO4 Alk. Acidity Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 77 0.07 30 0.07 167 27 36 35 3 65 8 0.28 0.16 0.28 4.2 0.14 0.04 0.51 55 150 78 0.70 50 bd 47 47 12 12 4 25 7 0.41 0.13 0.19 6.3 0.31 0.27 0.18 83 247 79 0.07 368 0.03 173 20 147 225 5 97 16 bd 0.32 0.31 3.4 0.15 0.27 1.26 134 419 80 0.03 20 0.13 153 27 20 14 3 54 11 bd 0.26 0.21 1.6 0.19 0.20 0.32 145 55 81 0.39 28 0.13 67 220 10 13 6 21 7 bd 0.54 0.19 2.6 0.38 0.13 0.15 69 238 82 0.04 41 0.06 160 33 12 22 3 60 9 bd 0.24 0.28 4.0 0.19 0.07 0.49 102 bd 83 0.40 20 bd 113 33 24 25 4 37 7 bd 0.38 0.17 5.2 0.24 0.22 0.23 8 128 84 1.20 88 0.30 140 40 24 28 4 67 13 bd 0.13 0.25 3.2 0.24 0.03 0.29 87 310 85 0.03 130 0.48 93 20 14 18 3 69 13 bd 0.89 0.28 3.1 0.17 0.18 0.40 164 275 86 0.30 20 0.13 167 40 55 41 5 59 9 bd 0.29 0.23 3.6 0.14 0.10 0.35 64 215 87 0.33 69 0.09 113 40 17 29 6 46 8 0.02 0.63 0.19 3.8 0.15 0.03 0.28 8 339 88 0.28 31 0.02 53 53 10 14 5 23 4 bd 0.25 0.20 4.9 0.24 0.06 0.22 58 268 89 0.20 39 0.06 147 33 10 14 4 57 9 bd 0.65 0.26 3.2 0.22 0.21 0.40 118 203 90 0.63 15 0.07 67 60 12 16 3 17 5 bd 0.48 0.18 4.0 0.21 0.15 0.18 82 212 91 0.10 46 0.06 160 40 14 7 2 68 11 bd 0.44 0.27 5.3 0.13 0.22 0.33 77 100 92 0.39 8 0.09 167 33 14 24 3 61 9 bd 0.42 0.24 3.8 0.13 0.14 0.34 119 198 93 0.30 33 0.01 133 33 10 8 2 53 10 bd 0.44 0.22 4.1 0.12 0.05 0.33 77 228 bd ----- values below detection limit. T.PO4 --- Total phosphate concentration \Alk. ----- Alkalinity All concentrations are in mg/L except nickel (µg/L), Zn (µg/L), and alkalinity and acidity (mg CaCO3/L) Shade River Watershed sites starts from 22 to 43. Summer 2006 data are from site number 1 to 43 while summer 2005 starts from 44 to 93.

136

Apart from the major ions measured in the filtered waters, some few trace ions were also measured within the Shade River Watershed. These are shown in table (5 – 3). These chemical species were below detection in most of the sites.

Table 5 – 3 Concentrations of the trace elements measured in the Shade River Watershed.

OEPA No. Site Number Cd Co Cr Cu Mo Pb Zn NH3 S09630 27.302006 22 167 6 7 50 bd 153 493 0.19 S09600 17.002006 23 167 bd bd bd bd 63 257 0.17 S09630 0.202006 24 210 bd 50 218 bd 259 395 0.11 S09630 9.102006 25 33 bd 20 32 bd 330 422 0.17 S09630 5.902006 26 110 bd 51 40 bd 188 486 0.23 S09633 2.902006 27 405 bd 20 188 bd 506 476 0.10 S09633 5.702006 28 213 bd bd bd bd 162 511 0.07 S09630 24.102006 29 203 bd 13 134 bd 231 494 0.19 S09630 25.902006 30 453 bd bd 19 bd 142 364 0.34 S09634 2.402006 31 88 bd 5 121 bd 305 634 0.05 S09641 0.402006 32 23 bd 10 26 bd 315 448 0.24 S09644 1.102006 33 25 bd bd 148 2 296 410 0.02 S09643 5.502006 34 113 bd bd bd bd 194 512 0.02 S09648 0.102006 35 79 bd bd 280 bd 100 502 0.10 S09643 10.402006 36 322 27 3 290 bd 335 252 0.11 S09643 9.002006 37 173 bd 37 bd bd 154 420 0.07 S09647 0.102006 38 501 bd bd 79 bd 255 675 0.06 S09646 0.202006 39 161 bd bd bd bd 303 351 0.01 S09640 11.602006 40 60 bd 20 bd bd 234 453 0.18 S09640 19.002006 41 217 bd bd bd bd 257 60 0.06 S09640 16.602006 42 257 bd bd bd bd 289 406 0.16 S09645 2.502006 43 229 bd bd bd bd 324 169 0.10

bd indicate values below detection. All the concentrations are measured in µg/L except NH3 (mg/L) OEPA--- Ohio Environmental Protection Agency

137

Table 5 - 4 Concentration of the chemical species measured in the unfiltered water samples within the WAP ecoregion.

Site NO3 SO4 T. PO4 Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 1 0.15 29 0.35 32 82 6 80 29 1.82 0.20 0.12 5.4 2.19 0.34 0.43 124 bd 2 0.11 21 0.19 43 119 10 96 36 1.06 0.14 0.20 3.3 0.63 0.25 0.52 bd 353 3 0.07 69 0.17 10 17 4 185 61 0.31 0.56 0.24 1.5 0.81 0.13 0.66 142 bd 4 0.05 47 0.24 37 173 9 181 53 0.74 0.13 0.30 2.2 0.42 0.31 1.35 182 bd 5 5.00 11 0.17 31 44 3 87 21 1.11 0.15 0.22 1.4 0.37 0.22 0.32 123 bd 6 0.09 32 0.22 10 83 8 90 36 0.48 0.54 0.22 4.1 0.32 0.20 0.40 bd 290 7 0.18 34 0.33 18 93 8 103 35 0.71 0.28 0.26 3.1 0.41 0.19 0.46 92 bd 8 0.12 26 0.30 13 85 7 67 25 0.49 0.60 0.14 3.3 0.27 0.26 0.26 bd 379 9 0.21 1153 0.33 32 33 4 218 118 7.88 4.03 0.19 5.6 0.45 0.37 0.90 163 bd 10 0.25 1873 0.36 25 44 8 237 240 0.24 5.61 0.09 4.9 0.42 0.30 1.53 499 598 11 0.18 47 0.42 35 36 7 150 73 0.62 0.25 0.27 0.8 0.58 0.11 0.70 82 bd 12 4.00 91 0.26 21 26 5 200 120 0.60 0.56 0.16 3.9 0.51 0.42 0.83 226 bd 13 16.00 27 0.20 189 182 4 162 39 0.56 0.12 0.17 2.1 0.53 0.26 0.42 187 308 14 0.10 2233 0.20 7 447 15 196 137 1.22 0.14 0.22 3.2 1.43 0.31 3.38 141 bd 15 0.09 1729 0.20 8 268 8 240 241 1.15 0.17 0.29 3.7 1.45 0.18 3.59 211 730 16 0.07 7 0.18 16 21 5 93 28 1.71 0.20 0.17 0.7 1.45 0.29 0.48 bd 378 17 0.14 11 0.18 8 7 4 109 43 0.31 0.18 0.14 2.4 0.31 0.17 0.26 149 bd 18 0.12 10 0.23 20 17 5 41 26 0.89 0.24 0.26 1.0 0.42 0.31 0.22 76 436 19 0.07 13 0.24 10 11 4 62 13 0.44 0.16 0.21 0.5 0.39 0.17 0.30 bd bd 20 0.60 6 0.19 26 20 5 41 10 0.30 0.15 0.13 0.3 0.31 0.27 0.30 bd bd 21 0.36 4 0.35 23 16 4 64 22 0.51 0.16 0.19 1.4 0.56 0.18 0.27 bd bd 22 0.13 13 0.18 16 105 8 113 25 0.41 0.15 0.15 3.5 0.58 0.22 0.43 167 324 23 0.15 9 0.29 14 106 8 112 25 2.32 0.32 0.28 5.0 1.74 0.23 0.49 145 bd 24 0.10 17 0.21 11 106 8 121 30 0.79 0.15 0.24 3.8 0.89 0.22 0.60 185 333 25 0.07 17 0.32 7 17 7 88 21 0.52 0.15 0.13 1.0 0.63 0.15 0.43 bd bd

138

Table 5 – 4 (Continued)

Site NO3 SO4 T. PO4 Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 26 0.08 13 0.23 10 18 4 88 20 1.42 0.19 0.15 0.5 0.72 0.36 0.40 bd bd 27 0.12 17 0.29 12 117 9 112 28 0.69 0.13 0.15 2.7 0.36 0.28 0.55 bd bd 28 0.09 14 0.25 10 20 6 84 18 0.42 0.17 0.19 0.8 0.53 0.16 0.44 bd 211 29 0.07 10 0.27 9 110 8 119 30 2.08 0.28 0.18 4.0 1.47 0.08 0.54 150 bd 30 0.12 7 0.20 16 105 8 109 27 1.40 0.42 0.20 4.8 0.83 0.16 0.49 197 bd 31 0.09 24 0.24 6 95 8 122 33 0.49 0.13 0.21 3.2 0.69 0.14 0.56 185 bd 32 0.19 3 0.29 16 117 8 100 26 1.45 0.24 0.24 4.8 1.10 0.17 0.48 148 bd 33 0.09 13 0.22 7 93 6 103 24 1.20 0.22 0.24 3.9 0.39 0.40 0.51 166 457 34 0.10 17 0.41 5 70 7 103 20 0.52 0.15 0.20 4.2 0.44 0.29 0.38 178 bd 35 0.08 13 0.34 4 13 5 69 11 0.91 0.23 0.14 2.1 0.53 0.21 0.30 141 bd 36 0.12 36 0.32 5 90 7 133 27 1.02 0.36 0.32 5.5 0.60 0.22 0.48 bd bd 37 0.13 14 0.25 9 96 7 108 24 0.52 0.29 0.14 4.0 0.38 0.19 0.41 77 bd 38 0.05 10 0.28 2 106 5 110 28 0.18 0.14 0.22 3.4 0.29 0.22 0.58 87 575 39 0.11 32 0.19 8 105 8 126 36 0.44 0.17 0.19 6.4 1.13 0.34 0.58 147 bd 40 0.12 27 0.38 6 89 6 107 25 1.21 0.44 0.12 5.1 0.93 0.12 0.38 242 bd 41 0.07 19 0.20 22 120 8 138 30 0.61 0.23 0.16 3.2 0.27 0.16 0.95 280 345 42 0.13 21 0.34 10 16 5 91 16 3.89 0.50 0.24 1.6 0.42 0.19 0.39 230 bd 43 0.11 10 0.29 4 109 7 105 23 0.56 0.15 0.20 3.8 0.47 0.16 0.44 177 bd 44 0.24 54 0.10 14 10 3 65 12 0.14 0.01 0.21 3.1 0.20 0.19 0.32 66 123 45 0.06 62 0.22 16 15 2 39 11 bd 0.04 0.23 4.7 0.14 0.07 0.37 47 143 46 0.39 57 0.11 10 29 3 48 11 0.65 0.42 0.18 3.3 0.38 0.14 0.34 8 72 47 0.03 25 0.21 10 7 2 28 6 0.18 0.13 0.13 3.8 0.17 0.06 0.23 121 159 48 0.03 28 0.04 15 8 2 63 9 0.43 0.41 0.22 4.8 0.16 0.09 0.31 144 185 49 0.14 42 0.07 19 9 2 63 9 0.04 0.34 0.23 4.0 0.24 0.20 0.29 63 269 50 0.18 318 0.10 11 43 5 114 41 0.02 1.63 0.23 3.9 0.37 0.13 0.89 132 177 51 0.18 231 0.07 10 15 3 114 30 0.49 0.54 0.18 3.8 0.34 0.10 0.50 91 113

139

Table 5 – 4 (Continued)

Site NO3 SO4 T. PO4 Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 52 0.04 361 0.07 14 11 2 124 44 0.94 0.28 0.13 6.2 0.19 0.09 0.53 148 345 53 0.04 31 bd 12 8 3 51 8 bd 0.32 0.26 4.4 0.29 0.11 0.26 97 130 54 0.18 17 bd 17 5 3 49 12 0.04 0.42 0.14 5.4 0.34 0.09 0.16 8 bd 55 0.20 22 0.11 13 8 2 19 5 0.15 0.42 0.17 4.1 0.21 0.09 0.23 64 104 56 0.32 303 0.07 12 46 4 102 22 0.07 0.41 0.18 5.0 0.21 0.18 0.79 8 267 57 0.04 25 0.28 132 58 3 66 12 0.04 0.49 0.27 4.1 0.16 0.09 0.50 105 347 58 0.04 51 0.06 47 14 3 65 9 bd 0.60 0.18 3.6 0.15 8.18 0.30 138 147 59 0.03 55 0.07 20 7 3 87 10 bd 0.45 0.19 5.3 0.15 0.16 0.39 98 110 60 0.16 26 0.13 10 9 2 58 9 0.09 0.35 0.19 4.1 0.16 0.16 0.35 43 132 61 0.03 100 0.14 24 15 3 57 14 0.06 0.33 0.20 4.4 0.19 0.23 0.46 74 339 62 0.07 87 0.09 10 14 5 60 10 0.83 0.46 0.19 2.1 0.44 0.18 0.26 8 105 63 0.03 117 0.10 29 92 3 73 12 0.22 0.29 0.21 4.3 0.14 0.16 0.72 112 225 64 0.07 21 0.09 14 26 2 54 11 1.08 0.65 0.20 5.3 0.22 0.17 0.47 142 72 65 0.18 167 0.14 18 43 4 69 15 0.27 0.35 0.19 4.6 0.19 0.08 0.44 136 186 66 0.22 58 0.07 11 19 4 39 11 1.33 1.73 0.21 5.2 0.22 0.19 0.23 60 86 67 0.07 25 0.04 34 28 3 29 9 0.49 0.56 0.19 2.6 0.31 0.17 0.36 99 102 68 0.09 22 bd 10 10 3 47 9 0.43 0.51 0.22 4.1 0.15 0.15 0.27 128 195 69 0.41 48 0.17 17 6 3 71 33 0.38 0.36 0.28 5.7 0.16 0.09 0.20 71 315 70 0.18 80 0.07 10 18 4 48 12 0.86 0.94 0.16 3.5 0.28 0.14 0.30 119 54 71 0.41 26 0.09 43 27 4 32 9 1.70 0.96 0.20 4.0 0.22 0.14 0.22 40 15 72 0.27 41 0.18 10 15 3 23 8 1.00 0.94 0.20 5.1 0.25 0.03 0.18 92 156 73 0.37 15 0.09 12 12 5 16 4 1.17 0.96 0.14 4.6 0.73 0.11 0.15 76 45 74 0.96 51 0.12 10 8 5 64 22 0.55 0.65 0.28 6.3 0.27 0.22 0.16 120 70 75 0.41 24 0.24 13 21 5 44 9 0.46 0.53 0.16 4.5 0.20 0.25 0.27 105 221 76 0.04 76 0.21 11 19 5 36 11 0.75 0.78 0.25 4.4 0.56 0.18 0.24 62 257

140

Table 5 – 4 (Continued)

Site NO3 SO4 T. PO4 Cl Na K Ca Mg Fe Mn Ba SiO2 Al Li Sr Ni Zn 77 0.20 33 0.06 37 34 3 66 9 0.23 0.26 0.19 4.3 0.20 0.10 0.50 8 11 78 1.59 50 0.17 10 12 5 26 7 1.20 0.17 0.23 6.3 0.44 0.14 0.17 130 261 79 0.04 353 0.02 163 226 5 104 16 bd 0.33 0.24 3.9 0.28 0.20 1.31 60 207 80 0.16 22 1.59 17 14 3 55 11 0.04 0.35 0.24 1.2 0.29 0.09 0.38 85 72 81 0.88 28 0.13 10 13 5 20 6 0.27 0.54 0.21 4.4 0.49 0.04 0.19 8 221 82 0.10 43 0.09 12 23 3 63 9 bd 0.10 0.26 4.2 0.22 0.27 0.54 82 118 83 0.28 21 bd 25 25 4 35 7 bd 0.39 0.16 5.1 0.55 0.17 0.26 88 65 84 0.35 95 0.24 24 29 5 69 14 bd 0.26 0.24 3.2 0.35 0.06 0.30 76 108 85 0.03 141 0.58 14 18 3 69 13 0.07 0.90 0.22 2.8 0.28 0.11 0.49 162 210 86 0.26 18 bd 51 41 5 60 9 bd 0.36 0.18 3.5 0.25 0.14 0.36 74 254 87 0.71 73 0.07 15 30 8 47 8 1.55 0.79 0.23 5.3 0.30 0.18 0.31 85 bd 88 0.28 32 0.08 10 15 4 23 5 0.04 0.31 0.17 5.1 0.56 0.06 0.20 120 391 89 0.22 40 0.06 10 15 4 57 9 0.04 0.72 0.20 1.5 0.29 0.10 0.45 118 242 90 0.35 15 0.06 11 16 4 17 5 0.65 0.49 0.17 4.4 0.32 0.15 0.15 106 122 91 0.04 43 0.09 13 7 2 71 11 0.20 0.58 0.19 5.2 0.25 0.06 0.33 118 147 92 1.20 27 0.08 17 25 3 62 9 bd 0.47 0.16 4.4 0.26 0.25 0.36 68 169 93 0.16 31 0.05 11 9 2 57 10 bd 0.48 0.24 4.6 0.14 0.14 0.36 78 212 bd ----- values below detection limit. All concentrations are in mg/L except nickel (µg/L), Zn (µg/L), and alkalinity and acidity (mg CaCO3/L) Shade River Watershed sites starts from 22 to 43. Summer 2006 data are from site number 1 to 43 while summer 2005 starts from 44 to 93.

141

Apart from the major ions measured in the unfiltered waters, some few trace ions were also measured within the Shade River Watershed. These are shown in Table (5 - 5).

Table 5 – 5 Concentrations of the trace elements measured in the unfiltered water samples taken from the Shade River Watershed.

OEPA No. Site Number Cd Cr Cu Mo Pb NH3 S09630 27.302006 22 bd bd bd bd 338 0.18 S09600 17.002006 23 bd bd bd bd 258 0.26 S09630 0.202006 24 627 bd 78 bd 390 0.10 S09630 9.102006 25 bd bd bd bd 210 0.10 S09630 5.902006 26 bd bd bd bd bd 0.16 S09633 2.902006 27 bd bd bd bd 417 0.11 S09633 5.702006 28 57 bd 94 bd 550 0.05 S09630 24.102006 29 bd bd bd bd 266 0.17 S09630 25.902006 30 955 bd 185 bd 259 0.35 S09634 2.402006 31 bd bd 281 bd bd 0.11 S09641 0.402006 32 bd bd bd bd bd 0.18 S09644 1.102006 33 bd bd bd 9 332 0.13 S09643 5.502006 34 bd bd bd bd 286 0.03 S09648 0.102006 35 bd bd bd bd bd 0.05 S09643 10.402006 36 bd bd bd bd 512 0.08 S09643 9.002006 37 bd bd bd bd bd 0.12 S09647 0.102006 38 bd bd bd bd 294 0.07 S09646 0.202006 39 bd bd 82 5 bd 0.14 S09640 11.602006 40 bd bd bd bd bd 0.19 S09640 19.002006 41 bd bd 233 bd 224 0.11 S09640 16.602006 42 bd bd bd bd bd 0.28 S09645 2.502006 43 bd bd bd bd bd 0.03

bd indicate values below detection. All the concentrations are measured in µg/L except NH3 (mg/L) OEPA--- Ohio Environmental Protection Agency

142

Table 5 – 6 Descriptive statistics for the measured ions (filtered samples) and the field parameters with their respective criterion for aquatic life ( WAP ecoregion)

Parameter Minimum Maximum Mean Standard deviation USEPA Critera

NO3 0.02 12 0.50 1.50 0.34 SO4 4 2233 129 392 860 Total PO4 0.01 0.93 0.20 0.16 0.05 Alkalinity 19 314 131 55 > 20 Acidity 5 220 34 29 ----- Cl 2 178 20 27 860 Na 5 427 50 62 ----- K 2 9 5 2 ----- Ca 16 240 84 48 ----- Mg 4 243 27 38 ----- Fe 0.02 6.30 0.40 1.00 1.00 Mn 0.11 5.89 0.50 0.70 0.10 Al 0.10 0.49 0.20 0.07 0.5 Ba 0.10 0.38 0.20 0.05 ---- Sr 0.06 3.57 0.50 0.50 ----

SiO2 0.10 20.2 3.53 2.22 ---- pH 6.2 8.2 7.48 0.47 6.5 - 8.5 TDS 71 3375 294 385 1500 EC 150 6370 579 723 750 DO 2 15 6.3 2.4 > 4.0

All the parameters are in mg/L except pH (unit-less), EC (µS/cm), and alkalinity and acidity in mg of CaCO3/L. ---- no available criterion for aquatic life. The USEPA criteria were obtained from USEPA, 1976 and 1986.

143

Table 5 – 7 Descriptive statistics for the measured ions (filtered samples) and the field parameters with their respective criterion for aquatic life (Shade River Watershed)

Parameter Minimum Maximum Mean Standard Deviation USEPA Criteria

NO3 0.03 0.31 0.12 0.07 0.34 SO4 4 29 13 7 860 Total PO4 0.17 0.55 0.28 0.10 0.05 NH3 0.01 0.34 0.10 0.10 2.20 Cl 2 20 8 4 860 Na 18 115 80 28 --- K 6 9 7 1 --- Ca 84 131 107 13 --- Mg 17 32 27 4 ---

SiO2 0.1 4.4 2.8 1.2 --- Al 0.15 0.49 0.23 0.08 0.5 Fe 0.03 6.30 0.41 1.30 1.0 Mn 0.11 0.47 0.22 0.10 0.1 Ba 0.15 0.38 0.22 0.05 --- Sr 0.34 0.87 0.48 0.12 Cu 121 218 30.1 45.7 Ni 48 274 155 63 Pb 162 506 121 96 Zn 257 634 445 111 < 0.11 pH 6.9 8.2 7.6 0.3 6.5 - 8.5 TDS 158 276 209 37 1500 EC 311 543 419 72 750 DO 3 13 5.7 2.8 > 4 Alkalinity 44 201 149 36 > 20 Acidity 5 39 22 7

All the parameters are in mg/L except Cu (µg/L), Ni (µg/L), Pb (µg/L), Zn (µg/L), pH (unit-less), EC (µS/cm), and alkalinity and acidity in mg CaCO3/L. ------indicate no available criteria for aquatic life. The USEPA criteria were obtained from USEPA, 1976 and 1986.

144

Table 5 – 8 Concentration of the elements analyzed within the sediment samples and the organic content (WAP)

Site Na K Ca Mg Fe Al Ba Li Mn Be Co Cr Cu Mo Ni Pb Sr Zn TOC 1 1494 2579 5168 4462 42767 20348 79 188 656 81 49 29 54 46 81 bd 25 134 2.0 2 1091 1852 5046 3592 17222 4832 58 128 604 34 19 14 33 bd 13 bd 18 48 2.8 3 803 655 4675 2680 20508 3595 69 95 528 36 25 10 15 bd 14 bd 23 30 0.3 4 871 1096 4992 3603 41617 6641 44 80 482 bd 20 15 13 4 18 bd 19 30 0.7 5 1068 1193 5373 3190 24367 5045 79 83 534 30 17 13 23 bd 16 bd 30 43 0.5 6 1340 13110 52955 13287 14552 12325 143 182 773 bd 26 27 42 11 35 34 195 64 0.9 7 1089 1183 4841 2908 21016 4305 32 93 656 50 19 13 10 bd 21 bd 15 55 1.3 8 911 2005 4620 3386 16921 5763 94 119 1963 47 52 14 29 10 52 26 31 80 3.5 9 625 898 4404 2470 62780 2760 47 66 473 34 14 8 14 3 13 4 24 27 1.1 10 837 2267 5764 5462 44262 14838 163 176 1410 90 44 29 54 13 31 bd 55 62 2.5 11 520 2102 5318 4371 42313 10270 78 165 987 59 27 22 45 bd 28 3 36 69 0.8 12 725 879 4360 2465 14742 2884 79 70 734 42 16 8 0 bd 11 7 18 31 0.4 13 554 1520 4435 2425 31405 3327 137 91 1380 42 23 12 27 bd 19 10 87 37 0.6 14 717 843 4382 2539 41085 3416 30 80 929 bd 26 7 16 bd 22 bd 14 50 0.7 15 862 2910 4623 3486 34965 6246 51 83 575 42 14 14 20 bd 16 bd 20 36 0.2 16 801 1584 4759 3886 43428 7502 77 130 785 47 20 19 19 bd 22 bd 14 49 0.3 17 859 1223 4633 3099 23005 6104 102 81 487 62 15 13 20 5 15 2 28 32 0.1 18 1005 1694 4649 3643 42677 9538 115 88 429 69 17 17 27 6 16 2 27 32 2.3 19 853 2495 13005 4984 21735 11238 97 172 1307 bd 36 28 58 bd 30 bd 41 78 0.3 20 1028 1253 6772 3585 21631 6759 62 81 469 bd 14 18 20 11 17 12 35 56 0.1 21 719 935 4451 2518 26769 2896 53 55 679 45 14 6 6 bd 10 2 21 29 0.2 22 731 1001 4452 2536 31748 3755 23 106 633 42 24 10 35 20 24 3 22 63 1.4 23 456 3381 5411 4614 14315 11691 131 135 578 73 26 27 36 8 28 bd 49 56 0.3 24 891 2005 4922 3080 49468 6226 40 184 934 41 29 17 38 3 40 bd 18 80 0.3 25 1047 2508 6965 4170 39551 8020 83 156 975 33 25 18 40 8 33 3 21 128 0.6

145

Table 5 – 8 (Continued)

Site Na K Ca Mg Fe Al Ba Li Mn Be Co Cr Cu Mo Ni Pb Sr Zn TOC 26 984 4233 5052 3859 19011 8795 78 84 404 81 23 16 15 8 21 8 32 44 0.3 27 1269 2127 5038 3311 45914 5280 57 188 1007 57 28 19 38 bd 34 7 24 86 0.3 28 1325 2215 5173 3453 24275 5552 38 92 370 54 14 14 22 bd 20 bd 14 53 0.2 29 1279 2345 5637 4578 14645 11718 219 183 1368 59 34 29 55 bd 37 bd 70 78 0.3 30 866 2770 5609 4481 13732 10959 212 176 2399 bd 35 26 59 17 36 bd 152 60 0.3 31 1250 2847 4940 3459 42010 7537 86 205 1076 bd 34 22 43 bd 32 bd 39 104 0.2 32 1126 1415 4739 4207 14881 10173 91 98 559 76 21 16 19 bd 20 bd 30 48 0.1 33 899 2115 4409 3012 23701 4309 46 139 515 39 21 15 28 bd 12 bd 11 40 0.2 34 887 7232 7866 5462 9098 15817 96 178 1444 67 41 33 43 10 38 6 32 76 0.5 35 1045 2241 23372 16023 14972 3366 48 117 426 bd 14 18 30 78 28 52 28 53 0.3 36 798 3647 4732 3335 17021 6801 80 185 683 67 37 26 53 300 74 bd 16 199 0.2 37 1156 3306 6537 5332 17860 18117 172 146 603 87 34 32 34 8 34 bd 57 60 0.2 38 785 2453 4618 3590 40868 6811 63 116 634 bd 17 16 29 bd 17 4 20 36 0.2 39 999 1038 4749 2754 40628 5108 38 82 519 73 22 11 22 bd 24 bd 23 41 0.3 40 821 7337 6612 5741 12868 15366 118 166 1999 86 47 27 41 bd 49 bd 52 79 0.2 41 884 3713 4996 4696 14397 9792 94 121 534 55 27 21 32 1 22 bd 21 47 0.3 42 599 2608 4974 4372 16139 10785 137 192 1269 70 39 26 46 10 35 14 50 77 0.2 43 1833 3092 15369 8169 10694 20495 145 175 2145 bd 79 32 58 23 90 43 118 168 0.2 44 430 3228 11012 5578 44101 22151 5 15 1258 bd 6 4 8 2 9 6 11 768 6 45 671 2899 2777 4801 59538 24364 124 252 1641 36 70 47 72 3 42 54 38 1026 6.9 46 375 1237 1047 1406 15037 11082 40 65 232 17 26 16 49 5 15 bd 30 318 2 47 441 2405 1975 3021 31846 28792 108 145 907 22 48 30 36 4 28 17 32 576 3.7 48 540 2580 3020 3310 27210 29900 109 127 550 16 49 33 35 6 29 1 45 480 2.8 49 524 1548 2482 1721 16829 19937 80 70 356 bd 18 38 26 3 19 0 24 238 7 50 495 2808 3234 3558 31960 28735 137 125 687 22 36 33 47 2 35 12 34 710 2 51 670 2400 3520 3800 29140 24360 53 147 1150 21 41 32 45 2 31 20 25 629 5.4

146

Table 5 – 8 (Continued)

Site Na K Ca Mg Fe Al Ba Li Mn Be Co Cr Cu Mo Ni Pb Sr Zn TOC 52 545 1995 2407 1730 25786 27132 155 103 1306 bd 43 21 30 4 34 bd 32 617 4.3 53 782 5678 4400 5384 28530 35986 243 129 556 bd 34 33 47 5 29 10 44 535 3.7 54 329 666 3799 2198 10692 9975 20 40 130 11 16 9 23 5 15 5 8 430 1.5 55 550 1790 2190 3280 27480 18280 95 112 930 20 37 27 29 4 26 bd 26 493 2.2 56 850 2753 3379 2376 29007 35986 127 144 843 31 52 30 48 5 47 14 39 1132 7.9 57 540 3210 3150 3350 32970 24360 123 149 730 24 50 31 48 3 37 7 34 899 5.3 58 716 2321 2884 1815 31579 2781 111 150 1415 17 44 35 45 5 29 15 32 626 3.8 59 513 3536 4341 5200 38460 33219 139 169 917 19 37 34 49 5 35 19 37 701 4.1 60 505 1133 1693 942 17896 7208 46 61 311 15 16 15 28 4 14 bd 21 247 1.8 61 528 1983 2265 2898 27806 12189 60 119 617 bd 27 23 29 4 24 17 25 568 6 62 380 1761 1680 1308 32303 25965 63 133 391 23 29 25 35 3 26 15 33 647 2.9 63 761 4877 23647 5580 51342 18277 154 232 1148 0 50 38 46 6 43 41 115 854 6.1 64 601 4485 17474 7070 28606 44895 118 132 259 0 39 35 28 4 35 30 63 850 5.8 65 586 1630 2633 2136 36706 30582 104 168 555 18 37 26 29 3 35 10 28 925 6.1 66 374 918 1549 785 19611 12575 36 84 210 23 35 15 26 3 18 bd 23 453 1.2 67 573 2924 2131 4217 24642 22271 144 115 316 19 41 33 45 4 30 19 34 583 4.9 68 503 1471 1592 1942 17972 27811 72 76 429 bd 21 15 37 4 17 1 22 344 2 69 587 1589 59302 10188 18201 13037 50 60 315 bd 22 16 34 11 34 67 29 751 3.8 70 435 737 1436 965 22698 15345 24 73 456 bd 27 14 48 3 19 bd 21 307 1.6 71 409 982 1473 951 31617 20424 49 117 843 bd 31 15 53 4 19 bd 20 460 1.7 72 504 623 2280 650 12483 16730 24 48 656 8 26 11 18 2 14 6 6 294 0.9 73 353 729 1730 799 10158 19039 93 114 360 bd 95 36 172 8 103 108 183 238 2.6 74 546 1630 51395 9674 76461 25041 119 347 227 14 63 59 83 67 153 100 20 2510 7.6 75 547 701 3018 1216 14275 21809 27 61 309 12 15 10 25 2 12 2 17 309 3.9 76 375 1802 3071 2176 28855 13960 7 145 344 22 32 3 17 22 35 bd 18 957 4.1

147

Table 5 – 8 (Continued)

Site Na K Ca Mg Fe Al Ba Li Mn Be Co Cr Cu Mo Ni Pb Sr Zn TOC 77 446 642 5427 1891 30207 21347 96 124 803 19 35 26 34 2 22 19 31 589 3.3 78 532 2053 4501 2345 33733 16269 74 163 424 bd 44 35 37 36 84 17 22 6428 4.8 79 901 5266 73853 8919 31427 25041 125 132 457 bd 33 30 30 3 33 34 220 578 6.6 80 527 2472 5309 3498 20297 14422 54 91 239 9 32 28 47 4 25 9 37 361 3.2 81 380 780 1035 806 17057 12113 36 70 461 10 20 19 26 3 18 bd 18 346 1.3 82 624 3549 11739 3768 31523 11651 149 168 457 17 50 37 40 5 32 25 69 645 4.5 83 541 556 1632 369 10387 24579 24 52 459 17 15 11 35 3 11 1 18 329 1.3 84 493 639 4601 1356 11226 17654 24 49 500 bd 16 9 29 3 14 13 20 270 1.4 85 609 2714 2670 3724 26873 29658 152 185 588 bd 79 37 80 17 68 75 99 798 1.2 86 418 1029 3867 1269 22012 19962 49 102 658 bd 38 19 37 3 27 16 21 753 2.9 87 425 776 1574 710 24680 18577 32 89 346 11 22 13 27 3 17 bd 21 772 1.1 88 494 533 2457 821 9244 17654 22 46 173 11 15 13 19 2 13 5 13 180 0.6 89 549 1439 1643 1424 12674 23194 57 63 1024 11 20 16 29 2 17 4 23 253 1.5 90 725 871 3705 1381 14199 17654 43 64 588 12 21 13 17 2 21 11 19 329 2.1 91 447 2476 2031 3283 20259 32666 103 91 528 13 33 22 47 3 23 bd 28 481 5.2 92 530 2544 2896 2470 24680 29899 117 165 683 19 40 34 39 5 30 14 40 673 2.8 93 446 3002 8537 4548 40823 23258 110 105 1178 20 34 25 37 4 25 bd 26 417 6.1

All the elements are in mg/Kg of dry weight, except TOC which is measured in %. Shade River Watershed sites starts from 22 to 43.

148

Table 5 – 9 Descriptive statistics for the streambed sediments taken within WAP

Element Minimum Maximum Mean Standard Deviation Na 329 1833 724 290 K 533 13110 2282 1753 Ca 1035 73853 7278 11915 Mg 369 16023 3601 2518 Fe 9098 76461 26996 12974 Al 2760 44895 15451 9495 Ba 5 243 85 49 Li 15 347 122 53 Mn 130 2399 740 449 Co 6 95 32 16 Cr 3 59 22 10 Cu 0 172 36 21 Ni 9 153 30 22 Sr 6 220 38 38 Zn 27 6428 413 734 TOC 0.1 7.9 2.3 2.2

All the elements are in mg/Kg of dry weight, except TOC which is measured in %.

Table 5 – 10 Descriptive statistics for the streambed sediments taken within Shade River Watershed

Element Minimum Maximum Mean Standard Deviation Na 456 1833 997 290 K 1001 7337 2983 1614 Ca 4409 23372 6644 4389 Mg 2536 16023 4738 2809 Fe 9098 49468 23991 13013 Al 3366 20495 9385 4707 Ba 23 219 95 55 Li 82 205 147 39 Mn 370 2399 958 590 Co 14 79 30 14 Cr 10 33 21 7 Cu 15 59 37 12 Ni 12 90 34 18 Sr 11 152 41 34 Zn 36 199 76 41 TOC 0.1 1.4 0.3 0.3

All the elements are in mg/Kg of dry weight, except TOC which is measured in %.

149

Table 5 – 11 Measured values for the biological indicators and the discharge rate for the streams within the WAP ecoregion, summer 2005 and 2006. These data were collected by the fish, macroinvertebrate, algae and hydrology teams of the STAR project.

OEPA No. Site IBI ICI PIBI Score (Scaled 0-100) Discharge (cfs) S01300 3.501997 1 12 - 70.35 10.60 S01340 0.901995 2 24 34 75.42 2.87 S06322 0.202000 3 32 30 69.58 0.81 S06500 2.301996 4 38 36 68.15 12.09 S06900 29.101996 5 39 18 65.33 2.36 S09500 108.901995 6 18 28 72.15 3.34 S09530 8.501995 7 37 32 59.93 4.41 S09575 0.201995 8 27 18 73.54 3.45 S17101 0.301997 9 16 20 70.19 4.67 S17403 0.201998 10 12 26 71.82 0.47 S17413 0.301998 11 18 38 67.76 0.84 S17414 1.701998 12 26 26 66.33 7.55 S17460 6.701998 13 35 24 63.10 123.13 S17870 6.201999 14 34 40 68.32 11.96 S17879 0.201999 15 26 - 53.04 1.88 S17890 0.801999 16 34 20 73.87 - S02545 2.202005 17 50 42 74.30 0.96 S02800 8.002005 18 54 28 63.66 1.51 S06420 2.202005 19 50 28 77.04 - S06440 0.902005 20 54 - 67.63 1.15 S17960 32.002005 21 56 46 65.11 9.34 S09630 27.302006 22 - 12 73.79 0.60 S09600 17.002006 23 - 34 57.99 4.67 S09630 0.202006 24 - - 67.72 0.90 S09630 9.102006 25 - 26 70.40 0.39 S09630 5.902006 26 - 40 60.15 0.26 S09633 2.902006 27 - - 59.01 0.21 S09633 5.702006 28 - 32 78.00 0.16 S09630 24.102006 29 - 32 71.74 1.30 S09630 25.902006 30 - 30 62.10 0.30 S09634 2.402006 31 - 38 65.46 0.51 S09641 0.402006 32 - - 67.84 - S09644 1.102006 33 - - 78.67 0.09 S09643 5.502006 34 - - 68.59 0.68 S09648 0.102006 35 - - 64.93 0.08 S09643 10.402006 36 - - 62.81 0.37 S09643 9.002006 37 - 40 66.50 0.63 S09647 0.102006 38 - - 60.85 - S09646 0.202006 39 - 14 52.94 0.26 S09640 11.602006 40 - - 69.76 0.33 S09640 19.002006 41 - - - - S09640 16.602006 42 - - 71.50 0.20 S09645 2.502006 43 - - - 0.18 All the highlighted values are for the Shade River Watershed

150

Table 5 – 11 (Continued)

PIBI Total OEPA No. Site IBI ICI (Scaled 0-100) Discharge (cfs) S06368 0.102005 44 52 - 64.99 - S01206 0.402005 45 44 - - - S09670 0.602005 46 48 - - - S06447 3.402005 47 54 - - - S06427 0.402005 48 54 - 74.07 0.01 S01131 0.502005 49 48 - - 0.06 S09704 0.802005 50 - - - 0.48 S06934 0.302005 51 52 50 57.04 0.18 S06360 1.102005 52 46 - 67.40 - S01006 1.102005 53 56 - 79.41 0.87 S02643 0.152005 54 56 38 65.95 0.79 S06444 1.702005 55 42 - - - S06408 0.102005 56 20 - 46.39 0.02 S06441 0.902005 57 54 - 65.78 - S06321 8.202005 58 46 44 61.82 - S06416 0.102005 59 50 - 75.13 - S06013 0.802005 60 56 - 71.31 - S06915 1.002005 61 44 36 73.53 0.01 S17308 3.502005 62 36 - 72.50 - S06504 1.402005 63 - 54 70.98 0.09 S06431 2.702005 64 48 - 60.34 - S06910 6.202005 65 50 - 66.30 0.25 S09007 3.302005 66 50 44 76.00 0.25 S06440 0.902005 67 54 24 76.75 0.08 S06420 2.202005 68 50 - 66.40 - S02545 2.202005 69 50 38 68.26 1.05 S06931 0.502005 70 44 40 63.93 0.53 S17973 1.802005 71 52 - 73.00 0.26 S02625 4.402005 72 54 50 82.54 0.62 S09300 27.202005 73 48 4 - - S02728 1.002005 74 - 48 73.45 0.16 S17960 32.002005 75 56 44 70.67 1.12 S02015 1.902005 76 52 - 65.87 0.02 S06458 4.002005 77 42 - 65.77 - S02800 8.001997 78 54 30 57.82 6.15 S06100 14.502005 79 52 26 70.83 0.29 S17044 3.502005 80 50 - 72.46 - S09300 12.602005 81 - 24 79.82 2.21 S06700 7.102005 82 48 36 76.20 0.15 S17960 12.402005 83 52 44 73.74 6.93 S17310 12.302005 84 46 44 64.03 0.73

151

Table 5 – 11 (Continued)

PIBI Score OEPA No. Site IBI ICI (Scaled 0-100) Discharge (cfs) S09100 5.802005 85 52 26 70.26 0.40 S08200 9.002005 86 50 34 64.09 98.82 S17502 0.602005 87 48 42 63.09 0.80 S09310 0.602005 88 54 46 74.96 0.76 S09630 8.102005 89 42 36 63.60 0.09 S02611 4.702005 90 56 28 62.88 0.95 S06351 0.102005 91 52 - 66.47 - S06327 0.802005 92 48 - 72.15 - S06427 1.102005 93 52 - 65.39 0.02

The data for the IBI, ICI and PIBI were collected by the fish, macroinvertebrate, and algae were collected by the biologist while the hydrology (discharge) were collected the hydrologist of the STAR projected. Shade River Watershed sites starts from 22 to 43. OEPA--- Ohio Environmental Protection Agency

Table 5 – 12 Descriptive statistics for the biological indices and flow rate in the WAP Ecoregion.

Minimum Maximum Mean Standard Deviation IBI 12 56 44 12 ICI 4 54 33 11 PIBI Total Score ) 46.39 82.54 68.10 6.50 Discharge (cfs) 0.0098 123.13 4.87 18.66

152

CHAPTER SIX--- DISCUSSION

6.0 Introduction

This chapter presents the analysis of the water and sediment chemistry results, the organic component of the sediments, and the biological indices of the streams within the WAP Ecoregion and the Shade River

Watershed that the biological team measured. The analysis includes the use of statistical tools to calculate the statistical variables for the field parameters and the ions for sediments and water samples. The statistical validity of relationships between variables such as correlation coefficients is tested. The strength of correlation or degree of association between two variables is evaluated by calculating the correlation coefficient, r. For the purposes of this study, the WAP and the Shade River are analyzed separately.

6.1 Analysis of the Spatial Variations for the Chemical Entities within the WAP

Ecoregion and the Shade River Watershed

6.1.1 Field Parameters

There were variations within some of the chemical species and field parameters measured as shown in Figures 5-1 to 5-32; and Appendix A

Figures A.1. to A.11. Some of the variables fell below the USEPA limit for the protection of aquatic life while others were above the limit.

153

Alkalinity measured within the WAP for 2005 ranged from 47 mg/L to 233 mg/L. The USEPA criterion for the protection of aquatic life for alkalinity is greater than 20 mg CaCO3 /L. Counties like Scioto,

Pike, Vinton, Hocking, Meigs, Washington, Monroe, Tuscarawas and

Coshocton had alkalinity concentrations lower than 20 mg CaCO3 /L.

Within the Shade River Watershed, the value for the alkalinity fell within the USEPA criteria for the protection of aquatic life.

Dissolved oxygen concentrations below the USEPA criterion for the protection of aquatic life of 4 mg/L were observed at some sites

(Figure 5-3). This might partially be due to the temperature at the time of sampling, low or no flow during the drought conditions that existed during the summer 2005 or the amount of contaminants in the stream.

DO within the Shade River Watershed fell within the USEPA criteria for the protection of aquatic life except sites 31 and 33, which had values lower than 4 mg/L (shown in Table 5-1).

The spatial distribution of the TDS and conductivity were virtually the same in both WAP and Shade River. The value for the TDS in the WAP fell within the USEPA criterion for the protection of aquatic life (1500 mg/L) except one site within Tuscarawas County which had TDS value of 3375 mg/L (Figure 5-5). The TDS value for the

Shade River fell within the USEPA criterion (Figure 5-6).

The pH measured within the WAP ranged from 6.2 to 8.2 (Figure

5-1; Table 5-7). Sites 2, 6 and 10 had pH values below the USEPA

154 criteria for the protection of aquatic life (6.5 – 8.5). Within the Shade

River Watershed, all the sites had pH values within the USEPA criterion (Figure 5-2). The low pH values measured within the WAP were situated within counties with coal mines.

6.1.2 Anions

Total phosphate was one of the main causes of impairment within the WAP and the Shade River Watershed. Within the WAP, the concentration of total phosphate was higher than the USEPA criterion for the protection of aquatic life (0.05 mg/L) as shown in Table 5-2, except eleven (11) sites within Scioto, Hocking, Washington, Monroe,

Carroll and Columbiana Counties, which had values ranging from 0.01 to 0.05 mg/L (Figure 5-15). Most of the counties that had high phosphate concentrations also had extensive farming activities (see

Figure 2–6). Within the Shade River, the concentration of total phosphate ranged from 0.2 to 0.5 mg/L (shown in Figure 5-16 and Table

5-2), which are far greater than the USEPA standard for the protection of aquatic life.

Chloride and sulfate concentrations were generally low within both the Shade River Watershed and WAP except some sites within

Noble and Tuscarawas Counties that had sulfate concentrations higher than USEPA standard for the protection of aquatic life of 860 mg/L, as shown in Figures 5-13 and 5-17.

155

Nitrate concentration within the WAP was within the USEPA criterion for the protection of aquatic life ( 0.34 mg/L) except few sites within Stark, Tuscarawas, Jefferson, Coshocton, Muskingum, Noble,

Monroe, Washington, Vinton, Scioto, Adams, Hocking and Jefferson

Counties (Figure 5-11) that had values higher than the criterion. Nitrate concentrations within Shade River Watershed were very low and they fell within the USEPA standard for the protection of aquatic (Figure 5-

12).

Bicarbonate concentration was calculated from the alkalinity measured in the 2005 samples. The dominant anion in both WAP and

Shade River Watershed was bicarbonate, followed by sulfate, chloride, nitrate, and total phosphate (see Figure 6-1 and Figure 6-2).

6.1.3 Cations

All the major cations (Ca, Mg, Na and K) had high concentrations at all the sites in the Shade River and the WAP ecoregion. The major cations are associated with the chemical weathering of carbonate or silicate minerals. The high calcium and magnesium concentration (see

Figure 5-23, Figure 5-25 and Figure 6-1 for the WAP; and Figure 5-24,

Figure 5-26 and Figure 6-2 for the Shade River) could be attributed to the limestone geology of the WAP. There was a similarity in the pattern of the spatial distribution of the measured calcium and magnesium concentrations in the WAP (Figure 5-23 and Figure 5-25) and the Shade

156

River Watershed (Figure 5-24 and Figure 5-26). Most of the high calcium concentrations and moderately high magnesium concentrations were measured within the Athens and Meigs Counties (Figures 5-23 and

Figure 5-25). There are some similarities in the spatial variation of the calcium and magnesium (Figure 5-24 and Figure 5-26) and calcium and sodium within the Shade River Watershed (Figure 5-20 and Figure 5-

24).

Potassium concentration was relatively high within the Athens and Meigs Counties (Figure 5-21) while the concentration of sodium was fairly low through the WAP except in Belmont and Noble Counties

(Figure 5-19). There was a similarity in the spatial distribution of the sodium and the potassium concentrations (Figures 5-19 and Figure 5-

21). The relatively high potassium and sodium concentrations could be attributed to the weathering of clay minerals and the micas within the sandstones.

Iron concentration measured in the Shade River Watershed and

WAP ecoregion fell within the USEPA criteria for the protection of aquatic life (1.0 mg/L) except three sites within Athens, Coshocton and

Tuscarawas Counties, which had values ranging from 1.00 to 6.30 mg/L

(Figure 5-27). The high iron concentrations in these counties were located within mined areas. The highest iron concentration was measured within Athens County (Figure 5-27). The presence of the iron in the WAP could be attributed to the shale and the coal geology while

157 the low iron concentrations measured could be attributed to the high pH of the waters or the buffering effect of the carbonates. Manganese is one of the causes of impairment within the WAP ecoregion and Shade

River Watershed. Manganese concentration ranged 0.11 to 5.89 mg/L in the WAP (Figure 5-29) and from 0.11 to 0.47 in the Shade River

Watershed (Figure 5-30). The range of values measured were beyond the USEPA criteria for the protection of aquatic life (Table 5-6). The high manganese concentration could be attributed to the local geology, discharge from abandoned mines or acidic soils. Manganese removal from mine discharge is quite expensive and difficult. Addition of alkaline chemicals or the geology of the area contributes in elevating the pH. Oxidation on the other hand helps in the precipitation of manganese hydroxide (Rose et al. 2003) at alkaline pH.

6.2 Composition of the Streamwaters in the WAP and Shade River Watershed

Ternary diagrams for the ions in the WAP ecoregion and the western and middle branches of the Shade River Watershed were plotted using the percentages of their milliequivalence. The diagrams showed that the predominant cation in the study area was calcium (Ca2+) while the

predominant anion was bicarbonate (HCO3 ), as shown in Figure 6-1 for

the WAP and Figure 6-2 for the Shade River. The hydrochemical facies

classification for the waters was the Ca–HCO3 type. This composition

158 might be due to the weathering of carbonates or silicate rocks (Eby

2004) in the presence of carbon dioxide and water:

2+ - CaCO3 (s) + H2 O (l) + CO2 (g) Ca (aq) + 2HCO3 (s)

8 Na0.75Ca0.25Al1.25Si2.75O8 (s) + 10 CO2 (g) + 15 H2O (l) 5 Al2Si2O5(OH)4 (s) +

+ 2+ - 12SiO2 (aq) + 6Na (aq) + 2Ca (aq) + 10HCO3 (aq)

6.3 Factors Controlling Water Quality within the WAP Ecoregion and the Shade

River Watershed

Factors that affect or control the quality of waters within the WAP

Ecoregion as well as the western and middle branches of the Shade

River Watershed include rock weathering, mining activities and/or agricultural activities. These are the main sources of pollution within the streams. For the excess concentrations produced by anthropogenic activities, the sources are generally classified as point and non-point sources of pollution.

6.3.1 Rock Weathering

As discussed in chapter 2, the WAP and the Shade River are made up of carbonate rocks (limestones) consisting of calcite and dolomite. Calcite is more soluble than dolomite. The dissolution of calcite is represented by the reaction:

2+ - CaCO3(s) + H2 O (aq) +CO2 (g) Ca (aq) + 2HCO3 (aq) .....equation 1

159

The weathering of carbonates results in the formation of calcium and bicarbonates ions as shown in equation 1. This reaction depends solely on the presence of carbon dioxide and water in the system. From equation 1, the solubility product for calcite (Kcalcite) is defined as:

2 2+ * a Ca − a HCO3 …………………….. equation 2 K calcite = PCO2

Where 2+ and − denote the activities of calcium and bicarbonate aCa aHCO3 ions respectively in solution (normally expressed in moles per kilogram

-3.5 of H2 O), while P is the partial pressure of carbon dioxide (10 atm CO2

o at 25 C). Since P and Kcalcite are both constants, equation 2 becomes: CO2

2 1 − = a HCO 3 2 + * a ca calcite PK CO 2

Taking the logarithms of the reactant and products in equation, it

becomes:

1 1 = + ) ……………equation 3 ( ) log ( ) (log2 a − log 10 10 10 HCO 3 2 + * a ca calcite PK CO2

Equation 4 becomes:

) = 2 )* - ) ………….equation 4 (log a 2 + (log K P CO (log2 a − 10 Ca 10 Calcite 10 HCO 3

A plot of the log of 2+ and − shows that most of the waters aCa aHCO3

within the WAP ecoregion are supersaturated with respect to calcite

160

(shown in Figure 6-3). For this plot, only the alkalinity values for the

2005 data was used.

Dolomite and calcite are mostly formed within the same vicinity but dolomite is formed when calcite dissolves in the presence of magnesium ions. This is represented by the equilibrium reaction:

2+ 2+ 2CaCO3(s) + Mg (aq) Ca (aq) + CaMg(CO3 ) 2 (s)……equation 5.

The equilibrium reaction for the formation of dolomite is represented

by the equation:

aCa 2+ K Dolomite = ………….………………equation 6 aMg 2+

Where 2+ and are the activities of calcium and magnesium ions aCa aMg 2+

respectively, while KDolomite is equilibrium constant for the formation

o of dolomite (10 2.0 ) at 25 C. Both activities in equation 5 are divided by

the square of the activity of hydrogen ion. Equation 5 becomes:

2 2 + = a Ca * a H + ………………….…. equation 7 K Dolomite 2 2 + a Mg a H +

To determine the stability field of both calcite and dolomite for the waters, equation 6 can be graphically demonstrated in ( aCa2+ ) versus log10 2 a H +

a Mg 2 + ( ) and can be rewritten in logarithm format as: log 10 2 a H +

161

aCa2+ aMg 2+ log ( ) = (log K ) + ( ) ………equation 8, 10 2 10 dolomite log10 2 + a H a H +

which represents a straight line as shown in Figure 6-4 and Figure 6-5

for the WAP and Shade River respectively. These figures show that the

waters are within the stability field of calcite. This is supported by the

high calcium and bicarbonate compositions of the waters as shown in

the ternary diagrams in Figure 6-1.and Figure 6-2.

The analysis of geochemical processes controlling waters within

the world cannot be done without mentioning Gibbs (1970) diagram.

Gibbs studied the salinity of most of the surface waters in the world

and concluded that the chemistry of the surface waters is affected by

atmospheric precipitation, rock weathering or evaporation and

crystallization processes. From his analysis, the atmospheric precipitation dominated processes are characterized by low Na+ and K+ with low TDS; while the evaporation-crystallization process is characterized by high concentrations of Na+ and Cl- with low Ca2+ concentration due to calcite precipitation. The rock weathering process is dominated by high concentrations of calcium, magnesium and bicarbonate ions with moderate TDS concentration. He plotted a graph

+ of TDS versus Na and obtained a boomerang–shaped graph + + CaNa 2+

(Huizenga 2004). Based on Gibbs (1970) criteria, the waters in the WAP

162 and Shade River Watershed were dominated by the process of rock weathering (Figure 6-6 and Figure 6-7).

According to the River classification scheme of Stallard and

Edmond in Eby (2004), the waters in the WAP and Shade River could be classified as type 3 rivers. According to this classification, rock weathering was the main process controlling the chemistry of the rivers dominated by calcium and magnesium ions, with an average TDS value

2+ 2+ greater than 250 mg/L and the value of ( + MgCa ) > 1 in most − 2− 5.0( HCO3 + SO4 ) cases.

6.3.2 Nutrients

Nutrient concentrations within the study areas were within the USEPA standard for the protection of aquatic life except total phosphate and nitrate at some sites (Figures 5-11 and 5-15; and Table 5-6) in the WAP and Figures 5-12 and 5-16 for some sites in the Shade River. High concentrations of nitrates were also measured at sites that had high concentration of total phosphate. The total phosphate concentration was in excess (beyond the USEPA criterion of 0.05 mg/L) at most of the sites. The high concentration of total phosphate has two possible origins:

1) erosion of rock residuals high in phosphate in the watershed and 2) compost of animal manure, inorganic fertilizers from farmland or household waste into streams. It is estimated that agriculture

163 contributes to about 60% of the impaired river miles and half of impaired lake acreage in the United States (Dufour et al. 2001).

6.3.3 Mining

The analyzed ions and field parameters that were associated with mining activities include iron, manganese, aluminum, zinc, sulfate, electrical conductivity, alkalinity and pH (FWPCA, 1969). Coal mines and abandoned underground mines within the area results in the AMD problems that characterize some areas. The mine spoils that are left after surface mining are transported into the streams resulting in the high concentration of manganese, aluminum and iron within the streambed sediments and some of the water samples. FWPCA (1969) suggests AMD impact criteria considering the following concentrations: iron (>0.5 mg/L), manganese (>0.5 mg/L), aluminum (> 0.3 mg/L), zinc (> 5 mg/L), conductivity (>800 µS/cm), sulfate (> 74 mg/L), alkalinity (< 20 mg/L) and pH (< 6). Although pH and alkalinity in most of the sites were beyond the limit for AMD impacted waters, other ions had concentrations suggesting AMD impact. Only Site 9 was consistent in suggesting a typical AMD impact (Tables 5-1 and 5-2).

The concentration of iron in the study area was within the criterion for the protection of aquatic life except sites 9, 26 and 71, which had concentrations of 5.16, 6.30 and 1.02 mg/L respectively.

These sites could be affected by AMD. Manganese was one of the

164 abundant elements that co-exist with iron. Manganese concentrations for all the sites were beyond the USEPA criteria for aquatic. High pH of the area resulted in the precipitation of manganese and iron in some site (Appendix B, Figure B.4.).

6.4 Statistical Analysis of the Chemical Species within the Streamwater Samples in

the WAP Ecoregion

Statistically, the ions and the field parameters were analyzed using parametric analytical tools at 95% confidence level (ρ = 0.05). The correlation matrix was obtained and the different correlation coefficients in the matrices were compared with the critical correlation coefficient determined by the test of significance of correlation (Swan and Sandilands, 1995). The critical correlation coefficient is 0.20

There is a strong positive correlation (r = 0.99) with a linear trend between TDS and EC as expected. The EC is approximately twice the value of the TDS. There is also a significant correlation between

TDS and the major ions: Ca (r = 0.60), Na (r = 0.36), Mg (r = 0.63) and

SO4 (r = 0.44). The correlation indicates a common rock source for the elements and the variability measured in the TDS is attributed to the

variation in the concentrations of Ca, Na, Mg and SO4 . Most of the

weathering capacity of natural water is due to the mild acidity produced

by dissolved carbon dioxide (Panigrahy and Raymahashay 2005).

165

SO4 is produced due to the oxidation of the sulfides within the rocks in the presence of water, resulting in the formation of AMD. The southeastern part of Ohio has high sulfate deposition (Amaning, 2006).

There is a positive correlation exists between sulfate and the major ions

(Mg [r = 0.88], Ca [r = 0.62], Na [r = 0.52]) and Mn (r = 0.56) as well

as with EC (r = 0.46) as shown on Table 6-1. The mobility of the major

ions in solution results in the increase in EC value. SO4 and EC are the most important indicators of stream conditions in a mined watershed and their concentration reflect the extent of the watershed disturbance

(Pond 2004). The composition of the waters, including sulfate and the major ions, reflects the geology and mineral assemblages in the area.

There is also a moderate and inverse correlation between SO4 and pH.

An increase in sulfate concentration corresponds to a decrease in the pH of the waters. This indicates that oxidation of sulfide minerals contributes to the concentrations of other major cations in solution.

pH correlates significantly with HCO3 (r = 0.44), DO (r = 0.53)

and Mn (r = -0.40) but weakly correlates with Fe (r = -0.10) as shown

in Table 6-1. This suggests that the concentration of Mn, Fe, DO and

HCO3 depends on pH. The inverse relationship between pH, and Fe and

Mn indicates that as the concentration of Fe and Mn increases, the pH decreases and vice–versa. Increase in pH in an oxidizing condition

results in the precipitation of Mn (DeNicola and Stapleton 2002) and Fe,

thereby reducing the concentration of Mn and Fe in solution since most

166 of the precipitant is adsorbed onto sediments. The precipitation of Mn and Fe is indicated by the reddish–brown coloration on sediments

(Appendix B, Figure B.4).

There is a significant correlation between bicarbonate and Ca (r =

0.31) and Mg (r = 0.18). This is expected since they are weathered products of the carbonates. Nitrate and phosphate are nutrient from point sources noted for the pollution of streams. High concentrations of these nutrients result in the process of eutrophication, which causes reduction in the concentration of DO in streams. Strong correlation exists between nitrate and total phosphate (r = 0.44), as shown in

Figure 6-8, indicating that both of them might be from the same source

(probably runoff from nitrogenous or phosphoric fertilizers used in reclamation activities or manure on farmlands). However, phosphate correlates with most major cations as compared to nitrate and chloride.

This suggests that there is another source of the production of phosphate. This might probably be due to the weathering of phosphate rich mineral within the area. Most of the nutrients in the waters are very reactive so they combine effectively with the major cations. This is evident in the strong correlation between phosphate and the major ions (Mg [r = 0.31], Ca [r = 0.48], K [r = 0.42] and Na [r = 0.31]).

Calcium correlates significant and positively with magnesium (r

= 0.82) as shown in Figure 6-9 and Table 6-1. This correlation indicates a common source rock (limestone).

167

6.5 Statistical Analysis of the Chemical Species within the Streamwater Samples in

the Western and Middle Branches of Shade River Watershed

Statistical analysis within the Shade is done at 95% confidence level (ρ

= 0.05) considering 22 total number of samples. The calculated t critical and r critical values calculated are 2.09 and 0.42 respectively.

There is a strong and significant correlation among most of the elements. Calcium correlates positively and significantly with Mg (r =

0.75) as shown in Figure 6-10 and Table 6-2, Na (r = 0.60) and Si (r =

0.44), indicating a common rock source. These elements may be related to the weathering of carbonates and silicates.

Alkalinity correlates negatively and strongly with sulfate (r = -

0.58) and silica (r = -0.44) and with Mn (r = -0.41). Sulfate and manganese are elements associated with the formation of AMD.

TDS correlates with EC (r = 0.98), as well as with K (r = 0.47) and

Mg (r = 0.45) pH correlates significantly with TDS (r = 0.53), EC (r =

0.53) and alkalinity (r = 0.41) but correlates negatively with Na (r = -

0.45), Si (r = -0.72), and Mn as shown in Table 6-2.

6.6 Streambed Sediment Chemistry within the WAP Ecoregion

Bulk sediment chemistry consists mainly of Na, K, Ca, Mg, Fe and Al with some trace elements including Co, Cr, Cu, Ni, Ba, Sr, and Zn. Fe,

Al, Ca, Mg and K are the dominant chemical species, accounting for

168 more than 96% of the elemental composition of the WAP sediments. The elemental abundance of the species are in the order of

Fe>Al>Ca>Mg>K>Mn>Na>Zn>Li>Ba>Sr>Cu>Co>Ni>Cr.

Iron is the most abundant element in the sediment samples, constituting about 47% of the elemental composition. This reflects the abundance of ironstone and pyrite in the area. Aluminum, which is less mobile, is normally associated with the weathering of the aluminosilicate rocks such as the feldspars (Post 1999). It is found in association with sodium, potassium and calcium. Sodium and potassium are also associated with clay minerals or shale. Magnesium and calcium are obtained from the weathering of carbonates within the study area.

Statistically, there is a significant correlation between Mg and Ca

(r = 0.74) as well as with Ba (r = 0.36), Li (r = 0.42), Cr (r = 0.35), Ni (r

= 0.33), and Sr (r = 0.41) as shown in Table 6-3. The correlation between Ca and Mg indicates a similar rock source (carbonates).

Mn correlates significantly with Co (r = 0.36), Cr (r = 0.20) and Sr

(r = 0.26) as shown in Table 6-3. Recent studies indicate that Mn oxides act as natural traps for heavy metals and the adsorption of these metals depends on the release of protons during chemical weathering of rocks

(Post 1999).

Na correlates significantly with Ca (r = 0.20), Mg (r = 0.44), K (r

= 0.32) and Al (-0.36), suggesting that these elements are present as weathered products of the silicates (feldspars) in the sandstones and

169 shales (clay). High concentrations of Ca, Mg and Na are found within the soil associations Gilpin – Upshur – Lowell – Guernsey and Coshocton –

Westmoreland – Berks. These soils are associated with Pottsville and

Allegheny Formations as well as Conemaugh Formation, which are noted for sandstone, shale and limestone geology. Dunkard Group which is located in the mid-eastern section of the WAP has the highest concentrations of the cations measured (Amaning 2006).

Aluminum correlates strongly and positively with most of the trace element including Ba (r = 0.35), Co (r = 0.44), Cr (r = 0.52), Cu (r =

0.32), Ni (r = 0.25), and Zn (r = 0.33) as shown in Table 6-3. These correlations indicate that the elements are by-products of weathering and they give an indication of a common rock source.

Correlation between pH and the sediment elements gives a negative and insignificant correlation except K (r = -0.23) and Co (r = -

0.29). Ca is the only element that gives a positive but insignificant correlation (r = 0.1) with pH (Table 6-3). High pH lowers desorption of the metals and possesses high buffering capacity against acidic condition that may be created as a result of waste accumulation (Tukura et al.

2007).

170

6.7 Streambed Sediment Chemistry of the Samples within the Shade River

Watershed

The concentration of the elements in the Shade River Watershed follows the same trend as that of the WAP Ecoregion but there is a slight difference. The elemental abundance of the species are in the order of Fe>Al>Ca>Mg>K>Na>Mn>Li>Ba>Zn>Sr>Cu>Ni>Co>Cr. Iron and chromium are the most and less abundant species respectively.

Statistically, Mg correlates significantly with Ca (r = 0.96), as shown in Table 6-4. The correlation between these elements indicates a similar rock source (carbonates). The high concentration of calcium and magnesium in the Shade River Watershed is associated with the Gilpin-

Upshur-Lowell-Guernsey soil associations. These soils are associated with the Pottsville and Allegheny Formations, which are noted for sandstone, shale and limestone geology.

Fe correlates negatively and moderately with Mg (r = -0.42) and

K (r = -0.49) as shown in Table 6-4. Mn correlates strongly and significantly with all of the trace elements [Co (r = 0.77), Cr (r = 0.60),

Cu (r = 0.79), Ni (r = 0.58), and Sr (r = 0.81)] as shown in Table 6-4.

The correlation indicates the tendency of manganese acting as a natural trap for the adsorption of the heavy metals. There is also a significant correlation among the trace elements.

Al correlates strongly and positively with most of the trace elements including Ba (r = 0.71), Mn (r = 0.59), Co (r = 0.78), Cr (r =

171

0.84), Cu (r = 0.44), Ni (r = 0.54), and Sr (r = 0.61), which are all by- products of weathering and they give an indication of a common rock source.

6.8 Relationship between TOC and Streambed Sediment Chemistry in the WAP

Total Organic Carbon (TOC) is the amount of organic matter within the sediment sample. It contributes to the acidity of natural water and sediments through the activities of biological organisms, organic acids formation and metal complexation (Tukura et al. 2007). It is formed through the decomposition of organic matters within the streamwater or streambed sediment. Organic matter, as well as fine-grained sediments, has high affinity for trace metals. The larger the quantity of organic matter in the sediments or the finer the grains sizes; the larger the surface area and the higher the sorption affinity of the sediments for trace metals.

Statistically, there is a strong and positive correlation between

TOC and Ca (r = 0.24), Fe (r = 0.33), Al (r = 0.63), Li (r = 0.21), Co (r =

0.36), Cr (r = 0.50), Cu (r = 0.20), Ni (r = 0.27) and Zn (r = 0.49) but a negative correlation with Na (r = -0.38) as shown in Table 6-4. Positive association of the chemical species with TOC may reflect the adsorptive tendency of the TOC to heavy metals, that is, the higher the amount of

TOC in the sediment, the greater the adsorptive capacity of the sediment.

172

6.9 Distribution Coefficient between the Chemical Species in the Streambed

Sediments and Streamwaters in the WAP Ecoregion

The distribution coefficient (Kd ) is an important parameter in the

determining the amount of dissolved contaminants in contact with a

geological material (soil, sediment or rock). It is defined as the ratio of

the concentration of the chemical species in sediment to the

concentration in water, that is,

Concentration dim entse Kd = Concentrationwater

K d is expressed in the units of mL/g as represented in Table 6-5. It is

affected by the presence of organic matter. The larger the amount of

organic matter within the sediment, the more contaminants is adsorbed.

The lowest Kd for the WAP is recorded by sodium and the highest by iron. The order for the calculated Kd is Fe>Al>Mn>K>Mg>Sr>Ca>Na.

For a given element, high Kd values are associated with area with high

amount of clay or fine sediments while the lowest are associated with coarse grained sediments. High content of organic matter also increases

the Kd .

6.10 Relationship between Sediment and Water Chemistry

The individual ions correlate significantly with each other in either

sediment or water samples but the case is different in correlating the

cations in the sediments to that of the waters (Table 6-7). There is no

173 clear relationship between the cations in the sediment and water samples but there is a significant relationship between aluminum in the sediment and the major cations in the water samples as well as with aluminum and strontium in the water sample. Aluminum correlates strongly and negatively with Na (r = -0.32), K (r = -0.44), Ca (r = -0.42), Mg (r = -

0.31), and Al (r = -0.38) as shown on Table 6-7. Aluminum is leached from sediments at low pH but precipitates when the pH increases

(Carroll et al. 2003).

There is a significant correlation between Na in sediment and Na

(r = 0.32), K (r = 0.66), Ca (r = 0.34) and Al (r = 0.29) in water (shown in Table 6-7). The concentrations of Ca and Mg in the sediments have a wide range in variation while those in the waters are restricted within narrow range (see Tables 5-2 and 5-8; Figures 6-9 and 6-10). This behavior is due to the solubility of the carbonates (calcite and dolomite) in the waters. The concentrations of these elements in contention are limited by their solubilities. On the other hand, there is no restriction in the concentration of these elements in the sediments since they are eroded, transported and accumulated in the sediments.

Iron in the sediment shows significant correlation with Ca (r =

0.25), Mg (r = 0.25), Mn (r = 0.23) and Sr (r = 0.24) in the water sample.

High Ca and Mg concentrations in the waters reflect high alkalinity, and high alkalinity promotes the precipitation of iron minerals resulting in high iron concentration in the sediments.

174

6.11 Relationship between PIBI and Water Chemistry

The PIBI calculated is in percentages based on a score from 0 to 100.

The calculated PIBI for the WAP varies from 46.36 % at site 24 to 82.54

% at site 46; with a mean value of 68.10 % and a standard deviation of

6.50 (Table 5-12).

PIBI depends solely on the PIBI metrics. The metrics include relative taxa richness, diatoms, cyanobacteria, dominant diatoms, acidophilic, eutraphentic, motile and chlorophyll.

There is no statistical relationship between water chemistry and

PIBI at 95% confidence level for the WAP as shown in Table 6-12 but there is a significant and major correlation between some of PIBI metrics and water chemistry. The abundance of diatoms and cyanobacteria in the water samples depends on the availability of Na, Ca, Mg, total phosphate and TDS as shown in Table 6-8. Diatoms correlate significantly with Na

(r = 0.27), K(r = 0.23), Ca (r = 0.33), Mg (r = 0.25) and TDS (r = 0.23).

Cyanobacteria also correlate significantly with the same elements

(except K), that is, Na (r = 0.21), Ca (r = 0.29), Mg (r = 0.21) and TDS

(r = 0.21) as shown in Table 6-8.

There is a significant relationship between total phosphate and the

PIBI metrics except the relative taxa richness, motile and dominant diatoms. Nitrate correlates strongly with acidophilic (r = -0.24) while chlorophyll depends largely on the abundance of chloride (r = 0.23).

Acidity correlates significantly with relative taxa richness (r = 0.21) and

175 motile (r = 0.27). The positive and strong correlations that exist among the individual PIBI metrics (Table 6-8) indicate a common association between them.

6.12 Relationship between IBI and the Water Chemistry

The IBI is calculated based on twelve metrics representing fish assemblages within streams. These metrics include the total number of native fish species, darter species, sunfish species, sucker species, intolerant species, percent abundance of tolerant species, proportion of omnivores, proportion of insectivores, top carnivores, number of individual in a sample, proportion of individuals as simple lithophilic spawners and proportion of individuals with disease, eroded fins, lesions and tumors.

IBI for the WAP varies from 12 at site 1 to 56 at site 21, 53, 54 and 90; with a mean value of 44.1 and a standard deviation of 12.0

(Table 5-12).

Statistically, the IBI correlates negatively with the major cations [Na (r =-0.35), K (r =-0.74), Mg (r =-0.24), and Ca (r =-0.48)], but positively with DO (r = 0.22) as well as Cl (r = 0.22), see Figure 6-

12. IBI correlates significantly and negatively with total phosphate (r = -

0.41) but positively with TOC (r = 0.42).

176

6.13 Relationship between ICI and Water Chemistry

The ICI is calculated based on a number of metrics as mentioned in chapter 1. The ICI measured ranged from 4 at site 73 to 54 at site 32; with a mean value of 33.25 and a standard deviation of 10.50 (Table 5-

12).

ICI shows significant and positive correlation only with acidity (r

= 0.28), pH (r = 0.23) and DO (r= 0.32) as shown in Table 6-12

Multivariate (stepwise) regression is used to develop an equation for the ICI based on the correlation between the chemical variables and

2 the ICI values. Based on Table 6-10, the model with Rp value of 0.17 is

used as the model for the equation. Therefore, the equation for the model

is represented as:

ICI = 0.154*(acidity) + 1.943*(DO) + 0.754*(pH) – 22.11

6.14 Relationship between the Biological Indices and Sediment Chemistry

The benthic organisms are normally affected by the chemistry of the

streambed sediments. Sediment can acts as a temporary sink for the

trapping of heavy metals in the waters.

Statistically, there is a significant relationship between the

biological indices and the sediment cations. IBI correlates negatively

with the sediment cations except Al and Zn (Table 6-13). IBI correlates

significantly with Na (r = -0.56), K (r = -0.27), Mg (r = -0.34), Li (r = -

177

0.42), Mn (r = -0.31), Al (r = 0.38), Ni (r = -0.24), Zn (r = 0.24) and

TOC (r = 0.42).

ICI on the other hand correlates significantly and negatively with

Al (r = -0.27). There is a moderate and inverse correlation between the

ICI and the trace elements.

PIBI shows no significant correlation with the major cation but correlates negatively with trace elements such as Cu (r = -0.31), Co (r =

-0.32) and Cr (r = -0.26) as shown in Table 6-13. This is inconsistent with the correlation between PIBI and the water chemistry. The PIBI metrics (except Acidophilic) correlate significantly with the sediment chemistry just like the case of the water chemistry. The metrics show no significant correlation with the major cations but correlate significantly and negatively with some of the trace elements in some cases (Table 6-

9).

178

Table 6-1 Correlation matrices for chemical species within the filtered water samples for the WAP ecoregion.

NO3 SO4 T. PO4 Alk. Acidity Cl Na K Ca Mg Fe Mn pH TDS EC DO

NO3 1

SO4 -0.05 1

T. PO4 0.44 0.13 1 Alkalinity 0.02 0.18 0.03 1 Acidity 0.03 0.02 -0.12 0.02 1 Cl 0.52 0.01 0.17 0.07 0.04 1 Na 0.14 0.52 0.31 0.41 -0.15 0.26 1 K -0.07 -0.01 0.42 -0.01 -0.16 -0.08 0.37 1 Ca 0.16 0.62 0.48 0.31 -0.16 0.10 0.58 0.35 1 Mg 0.07 0.88 0.31 0.18 -0.04 0.00 0.47 0.19 0.82 1 Fe -0.02 0.13 0.24 -0.08 -0.02 -0.03 -0.09 0.03 0.13 0.11 1 Mn -0.05 0.56 0.15 -0.25 0.05 0.00 -0.13 -0.08 0.30 0.53 0.30 1 pH 0.20 -0.24 -0.02 0.44 0.06 0.12 0.01 -0.06 0.02 -0.14 -0.10 -0.40 1 TDS 0.27 0.44 0.22 0.12 -0.06 0.14 0.36 0.05 0.60 0.63 0.02 0.17 0.09 1 EC 0.27 0.46 0.22 0.12 -0.06 0.16 0.36 0.04 0.61 0.64 0.02 0.18 0.11 0.99 1 DO 0.03 -0.01 -0.08 0.18 0.13 0.05 -0.18 -0.14 -0.09 0.00 -0.04 0.01 0.53 0.01 0.02 1

All the elements are in mg/L. The highlighted values are statistically significant at 95% confident level (|r| > 0.20) as given by the test of significance of the correlation (Swan and Sandilands, 1995). Alk---Alkalinity

179

Table 6-2 Correlation matrices for waters and field parameters within the Shade River Watershed. The highlighted values are statistically significant at 95% confidence level (|r|> 0.42; n =22 and ρ = 0.05), as given by the test of significance of the correlation (Swan and Sandilands, 1995).

NO3 SO4 T. PO4 Acidity Cl Na K Ca Mg Fe Mn Ba Si Al Li Sr pH TDS EC DO

NO3 1

SO4 -0.14 1

PO4 0.04 -0.03 1

Acidity -0.24 -0.32 -0.03 1

Cl 0.25 -0.24 -0.10 0.24 1

Na 0.32 -0.05 -0.08 -0.06 0.35 1

K -0.20 -0.32 0.05 -0.02 0.24 -0.08 1

Ca -0.14 -0.02 0.01 0.10 0.23 0.60 0.21 1

Mg 0.07 -0.09 -0.25 0.20 0.26 0.59 0.14 0.75 1

Fe 0.03 -0.14 -0.23 -0.12 0.04 -0.47 -0.01 -0.33 -0.28 1

Mn 0.32 0.22 0.32 -0.43 0.12 0.43 -0.24 0.32 0.05 -0.19 1

Ba 0.03 0.37 0.39 0.01 -0.28 -0.23 -0.06 -0.20 -0.46 0.06 -0.05 1

Si 0.25 0.27 0.29 -0.35 -0.06 0.73 -0.26 0.44 0.19 -0.49 0.64 0.11 1

Al -0.05 -0.24 0.02 0.01 0.16 0.27 0.39 0.22 0.16 -0.10 -0.14 0.03 -0.02 1

Li -0.10 -0.14 -0.16 0.08 -0.07 -0.14 -0.24 -0.08 -0.09 0.41 -0.27 0.03 -0.11 0.18 1

Sr -0.26 -0.22 -0.22 0.39 0.60 0.36 0.25 0.50 0.58 -0.09 -0.14 -0.44 -0.03 0.12 -0.03 1

pH -0.09 -0.19 -0.16 0.22 0.02 -0.45 0.27 -0.30 0.03 0.10 -0.65 -0.09 -0.72 0.05 0.03 0.00 1

TDS -0.28 -0.05 -0.27 0.32 0.33 -0.29 0.47 0.30 0.45 0.22 -0.38 -0.20 -0.59 0.02 -0.01 0.41 0.53 1

EC -0.25 0.01 -0.24 0.18 0.28 -0.30 0.48 0.27 0.44 0.17 -0.28 -0.23 -0.57 0.02 -0.09 0.30 0.53 0.98 1

DO -0.35 -0.24 0.11 0.13 -0.24 -0.53 0.14 -0.34 -0.33 -0.07 -0.32 -0.21 -0.38 -0.12 -0.13 -0.07 0.35 0.11 0.12 1

All the elements are in mg/L. Acid represents acidity; Alk represents alkalinity; and T. PO4 represents total phosphate.

180

Table 6-3 Correlation matrices for chemical species within the sediment samples for the WAP ecoregion. The highlighted values are statistically significant at 95% confidence level (|r|> 0.20; n =93 and ρ = 0.05), as given by the test of significance of the correlation (Swan and Sandilands, 1995).

Na K Ca Mg Fe Al Ba Li Mn Co Cr Cu Ni Sr Zn TOC pH Na 1 K 0.32 1 Ca 0.20 0.44 1 Mg 0.44 0.61 0.74 1 Fe 0.01 -0.02 0.14 0.12 1 Al -0.36 0.20 0.06 0.02 0.04 1 Ba 0.23 0.50 0.16 0.36 0.07 0.35 1 Li 0.28 0.43 0.27 0.42 0.45 0.18 0.56 1 Mn 0.31 0.29 -0.06 0.17 0.06 -0.04 0.44 0.39 1 Co 0.01 0.23 0.07 0.13 0.15 0.44 0.52 0.65 0.36 1 Cr 0.01 0.42 0.25 0.35 0.25 0.52 0.67 0.75 0.20 0.74 1 Cu -0.06 0.15 0.08 0.12 0.06 0.32 0.40 0.53 0.18 0.78 0.63 1 Ni 0.16 0.21 0.31 0.33 0.26 0.25 0.35 0.70 0.18 0.77 0.66 0.69 1 Sr 0.22 0.53 0.52 0.41 -0.10 0.16 0.54 0.32 0.26 0.46 0.39 0.49 0.34 1 Zn -0.28 0.00 0.13 0.00 0.24 0.33 0.06 0.27 -0.13 0.29 0.39 0.15 0.46 -0.03 1 TOC -0.38 0.09 0.24 0.07 0.33 0.63 0.19 0.21 -0.06 0.36 0.50 0.20 0.27 0.09 0.49 1 pH -0.02 -0.23 0.10 -0.06 -0.02 -0.14 -0.15 -0.18 -0.14 -0.29 -0.16 -0.22 -0.19 0.11 -0.08 -0.05 1

The elements are in mg/Kg except TOC (%).

181

Table 6-4 Correlation matrices for chemical species within the sediment samples for the Shade River Watershed. The highlighted values are statistically significant at 95% confidence level (|r|> 0.42; n =22 and ρ = 0.05), as given by the test of significance of the correlation (Swan and Sandilands, 1995).

Na K Ca Mg Fe Al Ba Li Mn Co Cr Cu Ni Sr Zn TOC Na 1 K -0.15 1 Ca 0.36 0.06 1 Mg 0.21 0.14 0.96 1 Fe 0.03 -0.49 -0.31 -0.42 1 Al 0.27 0.58 0.13 0.14 -0.59 1 Ba 0.12 0.26 0.01 0.10 -0.56 0.71 1 Li 0.09 0.29 -0.01 -0.03 0.02 0.33 0.44 1 Mn 0.22 0.40 0.12 0.09 -0.28 0.59 0.63 0.64 1 Co 0.39 0.42 0.20 0.11 -0.36 0.78 0.50 0.59 0.77 1 Cr 0.14 0.62 0.21 0.26 -0.60 0.84 0.77 0.65 0.60 0.72 1 Cu 0.13 0.22 0.12 0.08 -0.23 0.44 0.63 0.83 0.79 0.71 0.68 1 Ni 0.38 0.30 0.31 0.20 -0.27 0.54 0.34 0.57 0.58 0.86 0.62 0.72 1 Sr 0.27 0.12 0.21 0.20 -0.44 0.61 0.80 0.36 0.81 0.62 0.57 0.66 0.45 1 Zn 0.32 0.16 0.16 0.03 -0.04 0.26 0.14 0.60 0.37 0.64 0.44 0.66 0.88 0.18 1 TOC -0.23 -0.18 -0.04 -0.13 0.17 -0.24 -0.31 -0.22 -0.10 -0.12 -0.34 -0.02 -0.15 -0.15 -0.05 1

All the elements are in mg/Kg except TOC (%).

182

Table 6-5 Distribution Coefficient (mL/g) of some chemical species measured within sediment and water samples in the WAP Ecoregion.

Station Site Latitude Longitude Na K Ca Mg Fe Al Ba Mn Sr S01300 3.501997 1 39.45778 -82.20056 21 272 68 164 462576 66582 677 2864 70 S01340 0.901995 2 39.5478 -82.2819 10 208 56 104 116347 20162 275 3323 39 S06322 0.202000 3 39.62278 -81.35556 47 185 25 45 388228 12980 292 897 35 S06500 2.301996 4 40.0167 -80.7731 5 170 27 66 609154 24013 215 2648 14 S06900 29.101996 5 40.4783 -80.9136 25 405 63 157 148090 24098 480 3160 83 S09500 108.901995 6 39.3522 -82.3917 21 1727 630 395 100948 58402 576 1413 663 S09530 8.501995 7 39.2167 -82.4047 16 188 51 90 187974 14879 134 2288 36 S09575 0.201995 8 39.3803 -82.3983 13 316 74 146 75041 21843 862 3077 107 S17101 0.301997 9 40.58694 -81.37083 21 301 20 23 12157 12330 206 116 26 S17403 0.201998 10 40.58667 -81.50972 18 369 24 23 326302 39055 1098 239 34 S17413 0.301998 11 40.54472 -81.69361 14 353 35 59 338771 40475 344 3611 50 S17414 1.701998 12 40.50028 -81.61444 28 204 22 21 221883 11637 335 1380 23 S17460 6.701998 13 40.7186 -81.3456 3 329 27 59 285834 13016 776 8650 221 S17870 6.201999 14 39.8608 -81.6375 2 269 22 19 325806 12730 166 7670 4 S17879 0.201999 15 39.8478 -81.6714 3 466 19 15 374525 31887 241 4236 6 S17890 0.801999 16 39.8958 -81.5481 34 394 50 139 488811 51994 642 3351 29 S02545 2.202005 17 39.2975 -83.16595 123 326 42 71 74252 19759 738 2700 107 S02800 8.002005 18 39.04586 -83.12741 52 384 113 138 183069 36118 849 1710 153 S06420 2.202005 19 39.47404 -81.24243 75 730 208 379 358648 63480 413 7868 150 S06440 0.902005 20 39.63205 -81.05585 48 376 160 334 380317 42093 326 3772 115 S17960 32.002005 21 40.23831 -82.2508 47 232 71 119 193762 16695 262 4154 78 S09630 27.302006 22 39.2663 -82.0683 9 159 44 113 338482 21104 82 3889 52 S09600 17.002006 23 39.08737 -81.92498 5 594 52 205 111065 38076 875 1646 97 S09630 0.202006 24 39.10389 -81.92284 10 291 41 106 561983 17127 167 6780 32 S09630 9.102006 25 39.16705 -81.9402 57 373 77 198 870385 42508 391 7215 48

Shade River Watershed sites starts from 22 to 43.

183

Table 6-5 (Continued)

Station Site Latitude Longitude Na K Ca Mg Fe Al Ba Mn Sr S09630 5.902006 26 39.20634 -81.96862 53 622 58 197 3026 45789 334 3171 71 S09633 2.902006 27 39.20031 -82.00905 13 248 45 118 355675 10807 253 6629 44 S09633 5.702006 28 39.208 -82.05269 68 267 62 196 310945 28024 180 2459 32 S09630 24.102006 29 39.25207 -82.02538 13 294 48 154 104741 45718 1013 5711 129 S09630 25.902006 30 39.25295 -82.05099 8 403 51 161 58968 43093 962 6910 336 S09634 2.402006 31 39.27881 -82.0431 17 412 45 118 567548 40400 464 9051 90 S09641 0.402006 32 39.09914 -81.94148 10 200 49 162 65404 52140 460 2478 51 S09644 1.102006 33 39.09749 -82.01529 9 359 43 125 127081 20978 240 2325 23 S09643 5.502006 34 39.11315 -82.01635 10 1146 76 251 88137 45721 383 7515 91 S09648 0.102006 35 39.13135 -82.07428 17 390 267 926 127530 17745 128 2155 79 S09643 10.402006 36 39.13124 -82.07647 11 433 37 142 160666 29311 269 2079 40 S09643 9.002006 37 39.12622 -82.05617 13 531 61 229 122153 108764 908 2294 149 S09647 0.102006 38 39.1298 -81.98368 9 434 43 131 539273 43081 296 5553 32 S09646 0.202006 39 39.14703 -82.01043 14 153 41 87 410609 27828 251 4766 44 S09640 11.602006 40 39.15989 -82.02017 9 1174 66 231 134903 105244 623 4605 150 S09640 19.002006 41 39.17699 -82.12611 8 446 39 162 114670 42859 595 2860 24 S09640 16.602006 42 39.17111 -82.08354 6 448 38 161 315809 60846 660 2695 89 S09645 2.502006 43 39.19614 -82.09972 22 395 153 412 29063 75210 759 15586 289 S06368 0.102005 44 39.82889 -81.59583 43 1129 163 471 365676 223910 38 - 198 S01206 0.402005 45 39.46639 -82.08139 44 1206 63 408 - 209539 599 1578 97 S09670 0.602005 46 39.15420 -82.31360 13 395 23 120 34020 30817 191 747 86 S06447 3.402005 47 39.68026 -81.03075 59 1322 70 453 64965 179998 575 1106 149 S06427 0.402005 48 39.59194 -81.13694 71 1213 50 381 102602 199168 738 2619 146 S01131 0.502005 49 39.34440 -81.84780 57 703 42 189 - 99171 381 988 85 S09704 0.802005 50 40.01083 -81.57528 12 545 31 93 - 133403 510 446 38 S06934 0.302005 51 40.53140 -80.99030 47 836 31 127 144975 129920 528 2054 50

Shade River Watershed sites starts from 22 to 43.

184

Table 6-5 (Continued)

Station Site Latitude Longitude Na K Ca Mg Fe Al Ba Mn Sr S06360 1.102005 52 39.62056 -81.41389 50 820 22 45 - 220979 637 4837 62 S01006 1.102005 53 39.26810 -81.83750 98 2296 90 710 - 188849 1107 1855 150 S02643 0.152005 54 39.49720 -82.70250 60 295 77 195 - 57947 93 333 62 S06444 1.702005 55 39.66639 -81.04823 68 761 106 622 - 112593 450 2906 142 S06408 0.102005 56 39.47389 -81.31500 18 675 31 105 1198616 223385 531 2161 49 S06441 0.902005 57 39.61972 -81.05000 10 840 47 283 - 179943 369 2355 62 S06321 8.202005 58 39.57889 -81.33056 51 915 43 192 - 21816 558 3144 97 S06416 0.102005 59 39.53861 -81.24000 73 1482 52 539 - 275205 567 2477 112 S06013 0.802005 60 39.47111 -81.15000 54 517 30 107 - 43113 187 661 70 S06915 1.002005 61 40.63560 -80.83610 37 698 34 199 - 79378 340 1929 62 S17308 3.502005 62 39.71780 -82.07420 27 353 29 126 148862 82836 317 1028 132 S06504 1.402005 63 39.99310 -80.90110 8 1756 367 447 709144 166509 1183 3586 158 S06431 2.702005 64 39.59750 -81.21390 23 2579 334 715 709826 329832 545 360 144 S06910 6.202005 65 40.60190 -80.77170 14 396 43 144 - 230733 560 1735 63 S09007 3.302005 66 38.54860 -82.66250 21 246 40 77 41364 64320 201 127 107 S06440 0.902005 67 39.63167 -81.05694 19 940 69 495 98884 153818 693 789 100 S06420 2.202005 68 39.47530 -81.24080 51 635 36 210 52002 182991 282 1129 64 S02545 2.202005 69 39.30056 -83.17222 105 492 846 288 58074 89760 237 874 120 S06931 0.502005 70 40.51310 -80.90250 25 179 33 79 29119 116668 257 465 88 S17973 1.802005 71 40.22610 -82.16470 15 249 48 106 30982 125135 189 980 86 S02625 4.402005 72 39.42560 -82.57420 34 209 98 87 14794 96932 117 875 41 S09300 27.202005 73 38.92389 -82.79306 29 156 110 199 15607 97557 405 367 1209 S02728 1.002005 74 38.77360 -83.35080 66 350 804 452 134001 114964 444 378 120 S17960 32.002005 75 40.23830 -82.25110 28 146 69 138 43323 155925 138 552 73 S02015 1.902005 76 38.96833 -83.06861 21 392 88 176 83491 70280 29 547 88

185

Table 6-5 (Continued)

Station Site Latitude Longitude Na K Ca Mg Fe Al Ba Mn Sr S06458 4.002005 77 39.73690 -81.10830 13 230 84 223 107383 152694 343 5019 61 S02800 8.001997 78 39.04670 -83.12860 44 489 183 335 82296 53150 382 3260 118 S06100 14.502005 79 39.90920 -80.92420 4 1124 760 573 - 167162 410 1427 174 S17044 3.502005 80 39.52060 -81.70390 39 829 98 314 - 77874 260 920 115 S09300 12.602005 81 38.82420 -82.84780 29 134 50 120 - 32005 193 854 119 S06700 7.102005 82 39.76750 -80.93580 29 1113 194 419 - 60775 533 1902 140 S17960 12.402005 83 40.10810 -82.12720 21 138 44 52 - 102624 142 1209 77 S17310 12.302005 84 39.87920 -82.20610 17 164 69 101 - 72424 94 3844 67 S09100 5.802005 85 38.47860 -82.39780 34 826 39 295 - 174080 541 661 247 S08200 9.002005 86 40.76560 -80.72250 10 192 66 140 - 145449 217 2267 61 S17502 0.602005 87 40.30000 -81.74722 14 123 35 87 1019835 123796 170 549 75 S09310 0.602005 88 38.85750 -82.79640 35 104 109 194 - 73154 108 693 58 S09630 8.102005 89 39.16080 -81.94920 40 388 29 156 - 107236 219 1576 58 S02611 4.702005 90 39.21140 -82.71500 46 291 213 290 - 85042 236 1226 104 S06351 0.102005 91 39.59972 -81.30278 62 1313 30 305 - 242670 384 1199 86 S06327 0.802005 92 39.65583 -81.30028 22 930 47 266 - 236905 480 1626 118 S06427 1.102005 93 39.58417 -81.12917 53 1243 161 468 - 192767 501 2678 78

- no calculated distribution coefficient due to low concentrations within the waters.

186

Table 6-6 Descriptive Statistics for the distribution coefficient for the cations (mL/g) within the WAP samples.

Elements Minimum Maximum Mean Standard Deviation Na 2 123 31.0 24.3 K 104 2579 573.5 471.7 Ca 19 846 101.8 154.7 Mg 15 926 220.1 173.2 Fe 3026 1198616 249400.8 250614.0 Al 10807 329832 90148.5 72572.0 Ba 29 1183 423.8 261.0 Mn 116 15586 2765.2 2505.1 Sr 4 1209 108.6 141.9

Table 6-7 Pearson’s correlation coefficient (r) for the cations within the stream water (ppm) and streambed sediments (mg/Kg)in the WAP Ecoregion at 99% confidence level (n =93;| r|> 0.20) as given by the test of significance of the correlation (Swan and Sandilands, 1995). Na K Ca Mg Fe Al Ba Mn Sr mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg Na ppm 0.32 0.13 0.16 0.15 0.10 -0.32 0.05 0.21 0.22 K ppm 0.66 0.20 0.06 0.21 -0.08 -0.44 -0.01 0.19 0.10 Ca ppm 0.34 0.07 0.03 0.17 0.25 -0.42 0.12 0.26 0.02 Mg ppm 0.17 -0.02 0.00 0.08 0.25 -0.31 0.03 0.14 -0.04 Fe ppm 0.02 -0.01 -0.02 -0.04 0.12 -0.14 -0.10 -0.12 -0.03 Al ppm 0.29 -0.08 -0.10 -0.05 -0.03 -0.38 -0.08 0.06 -0.05 Ba ppm -0.10 0.13 0.23 0.24 -0.08 0.12 0.09 -0.15 0.15 Mn ppm -0.14 -0.06 -0.04 -0.02 0.23 0.05 0.10 0.06 0.06 Sr ppm 0.15 0.02 0.04 0.05 0.24 -0.20 0.00 0.07 0.03

187

Table 6-8 Pearson’s correlation coefficient between water chemical species and the PIBI metrics. The highlighted values are statistically significant at 95% confident level (ρ = 0.05, |r | > 0.42) as given by the test of significance of the correlation (Swan and Sandilands, 1995).

Relative % % taxa % Cyano- Dominant % % % Chlorophyll PIBI richness Diatoms bacteria diatom Acidophilic Eutraphentic Motile a1 NO3 -0.02 0.19 0.15 0.07 -0.24 0.10 0.00 0.13 0.04 SO4 -0.08 0.14 0.12 0.05 -0.01 -0.03 -0.09 0.01 0.02 Total PO4 -0.02 0.27 0.23 0.18 -0.17 0.10 -0.06 0.11 0.09 Alkalinity 0.17 0.19 0.13 0.27 -0.02 -0.16 -0.06 0.11 0.09 Acidity 0.21 0.04 0.09 0.02 0.18 0.09 0.27 0.01 0.15 Cl 0.04 0.08 0.13 0.12 -0.03 -0.06 -0.02 0.23 0.08 Na -0.03 0.27 0.21 0.11 -0.18 -0.03 -0.19 0.09 0.03 K -0.11 0.23 0.17 0.05 -0.13 0.12 -0.15 0.13 0.05 Ca -0.11 0.33 0.29 0.15 -0.11 0.05 -0.14 0.11 0.09 Mg -0.12 0.25 0.21 0.05 -0.07 0.06 -0.09 0.08 0.06 Fe 0.05 -0.07 -0.08 0.14 0.07 -0.09 0.04 -0.05 0.00 Mn -0.13 -0.08 -0.06 -0.04 0.07 0.03 -0.01 0.00 -0.03 pH 0.13 0.13 0.05 0.10 -0.09 -0.12 -0.08 0.12 0.03 TDS -0.04 0.23 0.21 0.02 0.04 0.05 -0.16 0.03 0.07 DO 0.00 0.00 -0.06 -0.01 -0.02 -0.07 0.07 -0.04 -0.02

Chemical species are measured in mg/L except pH (unit-less). Alkalinity and acidity are in mg CaCO3/L.

188

Table 6-9 Pearson’s correlation coefficient between sediment chemical species, TOC and the PIBI metrics. The highlighted values are statistically significant at 95% confident level (ρ = 0.05, |r| > 0.42) as given by the test of significance of the correlation (Swan and Sandilands, 1995).

Relative % % Chemical taxa % Cyano- Dominant % % % Chlorophyll PIBI Species richness Diatoms bacteria diatom Acidophilic Eutraphentic Motile a1 Na -0.13 0.15 0.11 0.07 -0.20 0.13 -0.03 0.15 0.03 K 0.01 -0.02 0.004 -0.002 0.08 0.09 -0.05 -0.05 0.01 Ca 0.06 0.03 0.10 0.07 0.12 0.06 0.16 0.06 0.11 Mg -0.005 -0.01 0.03 0.02 0.04 0.08 0.00 -0.04 0.02 Fe -0.03 0.07 0.07 0.11 -0.06 -0.05 0.08 0.11 0.04 Al 0.03 -0.40 -0.29 -0.12 0.18 -0.19 -0.07 -0.16 -0.15 Ba -0.05 -0.16 -0.11 -0.06 -0.03 -0.03 -0.05 -0.04 -0.09 Li -0.08 0.001 0.01 -0.05 0.01 0.03 -0.11 -0.07 -0.04 Mn -0.13 0.06 0.01 -0.06 -0.16 -0.10 -0.22 -0.08 -0.11 Co -0.28 -0.36 -0.31 -0.32 -0.08 -0.22 -0.23 -0.26 -0.32 Cr -0.13 -0.35 -0.29 -0.24 -0.03 -0.16 -0.17 -0.25 -0.26 Cu -0.26 -0.30 -0.29 -0.23 -0.11 -0.27 -0.28 -0.18 -0.31 Ni -0.17 -0.22 -0.15 -0.15 -0.03 -0.10 -0.14 -0.23 -0.19 Sr -0.17 -0.11 -0.10 -0.12 -0.14 -0.10 -0.11 -0.01 -0.14 Zn 0.01 -0.22 -0.09 -0.02 0.15 -0.10 0.15 -0.22 -0.05 TOC -0.02 -0.33 -0.23 -0.14 0.18 -0.18 0.07 -0.20 -0.12

Chemical species are measured in mg/L except pH (unit-less). Alkalinity and acidity are in mg CaCO3/L.

189

Table 6-10 Regression statistics for building a model in determining the ICI equation for the water samples.

2 Model SSR SSD SST RP ICI – Acidity 2364.542 28560.19 30924.73 0.08 ICI – pH 1613.958 29310.77 30924.73 0.05 ICI – DO 3258.8 27665.93 30924.73 0.11 ICI – Acidity, pH 3774.842 27149.89 30924.73 0.12 ICI – pH, DO 3390.165 27534.57 30924.73 0.11 ICI – Acidity, pH, DO 5128.406 25796.33 30924.73 0.17

SSR = Sum of square for regression SSD = Sum of square for the residuals SST = Total sum of squares 2 RP = Coefficient of multiple determinations

Table 6-11 Analysis of variance (ANOVA) for the model that predicted the equation for the ICI.

df SS MS F Significance F Regression 3 5128.41 1709.47 5.90 0.001 Residual 89 25796.33 289.85 Total 92 30924.73

190

Table 6-12 Correlation matrices for chemical species within the filtered water samples (mg/L) and the biological indices within the WAP ecoregion. The highlighted values are statistically significant at 95% confidence level (|r|> 0.20; n = 93 and ρ = 0.05), as given by the test of significance of the correlation (Swan and Sandilands, 1995).

IBI ICI PIBI NO3 0.06 0.03 0.04 Total PO4 -0.41 -0.003 0.09 SO4 -0.06 0.03 0.02 Alkalinity -0.15 0.18 0.09 Acidity 0.04 0.28 0.15 Cl 0.22 0.05 0.08 Na -0.35 0.01 0.03 K -0.74 0.03 0.05 Ca -0.48 0.01 0.09 Mg -0.24 0.06 0.06 Fe -0.14 0.11 0.001 Mn -0.03 0.05 -0.03 pH 0.02 0.23 0.03 TDS -0.10 0.10 0.07 DO 0.22 0.32 -0.02

Table 6-13 Correlation matrices for the chemical species in the streambed sediment samples (mg/Kg) and the biological indices within the WAP ecoregion. The highlighted values are statistically significant at 95% confidence level (|r|> 0.20; n = 93 and ρ = 0.05), as given by the test of significance of the correlation (Swan and Sandilands, 1995).

IBI ICI PIBI Na -0.56 -0.01 0.03 K -0.27 -0.18 0.01 Ca -0.09 0.16 0.11 Mg -0.34 -0.08 0.02 Fe -0.11 -0.05 0.04 Al 0.38 -0.27 -0.15 Ba -0.18 -0.14 -0.09 Li -0.42 -0.12 -0.04 Mn -0.31 -0.11 -0.11 Co -0.02 -0.18 -0.32 Cr -0.08 -0.16 -0.26 Cu -0.06 -0.15 -0.31 Ni -0.24 -0.09 -0.19 Sr -0.09 0.01 -0.14 Zn 0.24 0.04 -0.05 TOC 0.42 -0.11 -0.12

191

2+ Mg 2- SO4

2+ - - Ca + + Cl HCO Na +K 3

Figure 6-1. Ternary diagrams for the concentrations (milliequivalence in %) of the dominant ions in waters collected within the WAP Ecoregion.

2+ 2- Mg SO4

2+ - Ca + + Cl - Na +K HCO3

Figure 6-2. Ternary diagram for the concentrations (milliequivalence in %) of the dominant cations in waters collected within the western and middle branches of the Shade River Watershed.

-2.0 192 -3.4 -3.3 -3.2 -3.1 -3 -2.9 -2.8 -2.7 -2.6 -2.5 -2.2 Equilibrium line -2.4

-2.6

-2.8 (Ca)

a -3.0

Log Calcite supersaturation field -3.2

-3.4

Calcite undersaturation field -3.6

-3.8

-4.0 Log a (HCO3)

Figure 6-3. Phase diagram for the saturation field of calcite for the waters within the WAP Ecoregion using 2005 data.

15.0 2 R = 0.9698 14.0

Calcite stability field 13.0

(Ca/H2) 12.0

a Dolomite stability field Log 11.0

10.0 Equilibrium line

9.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 Log a(Mg/H2)

Figure 6-4. Stability field of calcite and dolomite for the waters within the WAP Ecoregion.

193 14.0

Equilibrium line 13.5

13.0 Calcite stability field

) 2 12.5

Log(Ca/H 12.0 Dolomite stability field

11.5

11.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 Log(Mg/H2)

Figure 6-5. Stability field of calcite and dolomite for the waters within the Shade River Watershed.

10000

EVAPORATION/ CRYSTALLIZATION 1000

L) / 100 ROCK WEATHERING

TDS (mg

PRECIPITATION

1 0 0.2 0.4 0.6 0.8 1 Na+/(Na++Ca2+)

Figure 6-6. Diagram for the dominant process controlling the water chemistry in the WAP Ecoregion (After Gibbs 1970).

194

10000 EVAPORATION/ CRYSTALLIZATION

1000

WEATHERING

100

TDS (mg/L)

PRECIPITATION

0 0.2 0.4 0.6 0.8 1 + + 2+ Figure 6-7. DiagramNa for/(Na the+Ca dominant) process controlling the water chemistry in the western and middle branches of Shade River Watershed (After Gibbs 1970).

1.0

0.9 R2 = 0.1914 0.8

0.7

0.6

0.5

0.4 0.3

Total Phosphate (mg/L) 0.2

0.1 0.0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0

Nitrate (mg/L) Figure 6-8. Diagram of total phosphate against nitrate.

195

300

R2 = 0.8554

250

200

150

(mg/L) Mg 100

0 0 50 100 150 200 250 300 Ca (mg/L)

Figure 6-9. Variation in the concentrations of calcium and magnesium for the waters in the WAP Ecoregion.

33 R2 = 0.5689 31

(mg/L) Mg 21

15 80 90 100 110 120 130 140 Ca (mg/L) Figure 6-10. Variation in the concentrations of calcium and magnesium for the waters in the Shade River Watershed.

196 300

250

200

150

Ca (mg/L) 100

0 0 20,000 40,000 60,000 80,000

Ca (mg/Kg) Figure 6-11. Variation in the concentration of Ca in the streambed sediment and the stream water in the WAP Ecoregion.

140

130

120

110

Ca (mg/L) 100

4000 8000 12000 16000 20000 24000 28000

Ca (mg/Kg) Figure 6-12. Variation in the concentration of Ca in the streambed sediment and the stream water in the Shade River Watershed.

197 300

250

200

150

Mg (mg/L) 100

0 2,000 4,000 6,000 8,000 10,000 12,000 14,000 16,000 18,000 Mg (mg/Kg)

Figure 6-13. Variation in the concentration of Mg in the streambed sediment and the stream water in the WAP Ecoregion.

31 29

27 25

23 Mg (mg/L) 21

19 17

15 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 Mg (mg/Kg)

Figure 6-14. Variation in the concentration of Mg in the streambed sediment and the stream water in the Shade River Watershed.

198

Figure 6-15 Map of the location of underground mines within Ohio

(Assessed at http://www.ohiodnr.com/website/geosurvey/omsiua/home.htm).

199

CHAPTER SEVEN--- CONCLUSIONS AND RECOMMENDATIONS

7.0 Conclusions

The hydrogeochemical investigation of the streamwater within the WAP and Shade River Watershed indicates that the predominant chemical species in the water type is Ca – HCO3 . This is based on a trilinear plot

+ of the major ions. Plot of TDS versus Na (following Gibbs, + + CaNa 2 +

1970) and river classification scheme of Stallard and Edmond in Eby

(2004) indicate that rock weathering is the main process controlling the

chemistry of the waters within the streams. High concentrations of Ca,

Mg, and HCO3 suggest that chemical weathering of the carbonates is

the predominant process resulting in the production of these ions.

However, the presence of K, Na and other ions suggests that weathering of silicates is also important. The mineral stability analysis of the waters indicates that the waters fall within calcite stability field of the equilibrium diagram. The waters are supersaturated with respect to the concentration of calcium and bicarbonate ions for saturation with calcite.

The analyzed waters within the Shade River Watershed are of good quality as compared to that of the WAP ecoregion. The range of concentrations for the chemical species within the Shade River

Watershed is satisfactory for the survival of biological species except dissolved oxygen, iron (one site), manganese and total phosphate while

200 the main sources of impairment in some streams within the WAP include dissolved oxygen, electrical conductivity, total dissolved solids, alkalinity, pH, iron, manganese, total phosphate, sulfate and nitrate.

The concentrations of total dissolved solids and electrical conductivity are high at areas impacted by mining activities where

AMD inputs are occurring. The concentration of dissolved oxygen at some sites is low due to no or low flow conditions experienced during the 2006 drought season, the presence of contaminants in the stream and/or due to the process of eutrophication. pH of the area ranges from neutral to alkaline with only one site having value below the USEPA criteria for the protection of aquatic life. The pH range of the waters can be attributed to the buffering effects of the limestone geology, which indicates that most of the sites are less impaired. However, the sampling sites were selected considering the presence of fish. In this way, sites that are deeply impacted and have no fish were not considered.

The concentrations of iron and sulfate are low in the Shade River

Watershed except sites that had mining problems or areas characterized by acidic soils. The ions of much concern within the area of study are manganese and phosphate. These elements had concentrations above the

USEPA criteria for the protection of aquatic organisms. The high

201 concentration might be due to the acidic nature of the soils, geology of the area or mining activities. The buffering effects of the carbonate can be a problem because it facilitates the precipitation of manganese in the sediments at alkaline pH. Phosphate on the other hand is an important nutrient but high concentrations results in the process of eutrophication which reduces the concentration of dissolved oxygen within the stream.

Most of the sites have total phosphate concentrations beyond the

USEPA criteria for the protection of aquatic life (0.05 mg/L). The high concentration of the total phosphate can be attributed to two possible sources. The first source is obtained from the strong correlation between nitrate and the total phosphate which indicates a non-point source for both (that is, probably from runoff of nitrogenous phosphoric fertilizers or manure used on the farmlands) while the second source is through the chemical weathering of mineral such as apatite within the rocks.

The correlation between the streambed sediments and streamwater indicates that the concentrations of calcium and magnesium within the water samples are limited within a short range while that within the sediment samples have a wider concentration range. The restriction in the water samples is due to the solubility of the carbonates within the waters while the wide range in the sediments indicate the transport of sediments of high concentration to the study area.

202

The biological indices show significant relationship with some elements within the waters. IBI correlates negatively with total phosphate, sodium potassium, calcium and magnesium but shows positive relationship with chloride and dissolved oxygen. ICI on the other hand correlates positively with pH, acidity and dissolved oxygen.

PIBI shows no significant correlation with water chemistry but the PIBI metrics show significant and strong correlations with the water chemistry. This implies that the values of the PIBI for the waters depend on some of the major cations. With the sediment chemistry, IBI correlates significantly and negatively with sodium, potassium, magnesium, lithium, manganese, cobalt and nickel but shows positive and significant correlation with aluminum, zinc and total organic carbon. PIBI shows a negative correlation with cobalt, chromium and copper while ICI correlates significant with only aluminum.

7.1 Recommendations

The relationship between addition of lime or other chemical species for remediation purposes in streams affected by AMD and the trace elements should be studied because addition of the chemical species control the pH of the water and also reduce the concentration of iron, but it results in the precipitation or increased concentrations of trace elements such as manganese, mercury and arsenic.

203

Titration is a very important process in determining the alkalinity or bicarbonate concentration of the streamwater. In the future, it would be advisable to do titration in the laboratory rather than the field. Most of the titration values measured for summer 2006 was below the expected value due to mechanical error from the digital titrator or the conditions under which titration was done.

Shallow waters have high concentrations of dissolved oxygen as it moves. It reacts with the rocks and the soils but the concentrations of the ions depend on climatic conditions. Groundwater or shallow groundwater has high TDS concentration because it has a long time to react with the rocks or soils in the subsurface as it percolates through before feeding the surface waters. In consequence, the installation of wells closer to streams for the investigation of streams and groundwater interaction and the water balance of the watershed are recommended.

High concentration of fluoride in groundwater can be of toxicological and geo-environmental issue. A typical example is high concentration of fluoride in groundwater has resulted in a disease called fluorosis in India during the past decade (Madhavan, 2001).

Recent research in sediments indicates that fluoride acts as a trap for the various toxic metal contaminants in an estuarine environment

(Krumgalz et al., 1990). In view of this, it would be important if the

204 analysis of fluoride, boron and other anions are added to the list of ions analyzed.

Heavy metal concentration is associated with urban runoff.

Therefore, it is recommended that an education or training program should be implemented to sensitize the population about the effect of runoff on aquatic organism and problems of bioaccumulation which in the future affects the health of the people. This educational program should involve interns from local universities to help clean up the various creeks, as well as to be involved in door to door sensitization programs. The establishment of sub-watershed groups with various structures would be of great help to the sensitization program and the mitigation of the problems related to non-point source pollution.

205

REFERENCES

1. Amaning, K., 2006. Streamwater and Sediment Chemistry of Ohio’s Western

Allegheny Plateau Ecoregion and their Relation to Aquatic Life. Ms Thesis Ohio

University, Athens – Ohio.

2. Boult, S., Collins, D. N., White, K, N., and Curtis, C. D., 1993. Metal Transport

in a Stream Polluted by Acid Mine Drainage – the Afon Goch, Anglesey, UK,

Environmental Pollution 84: 279 – 284.

3. Brant, R. A., 1964. Geological Description and Effects of Strip Mining on Coal

Overburden Material. The Ohio Journal of Science 64(2): 68 – 69.

4. Brant, R. A. and DeLong, R. M., 1960. Coal Resources of Ohio. Ohio Div. Geol.

Survev Bulletin 58, 245 pp.

5. Burton, C. A., Brown, L. R., and Belitz, K., 2005. Assessing Water Source and

Channel Type as Factors Affecting Benthic Macroinvertebrate and Periphyton

Assemblages in the Highly Urbanized Santa Ana River Basin, California:

American Fisheries Society Symposium 47: 239–262.

6. Carlson, E. H., 1991. Minerals of Ohio: Ohio Division of Geological Survey

Bulletin 69, 155 pp.

7. Carroll, K., Lopez, D.E.L., and Stoertz, M., 2003. Solute Transport at Low Flow

in an Acid Stream in Appalachian Ohio. Air, Water and Soil Pollution 144: 195 –

222.

206

8. Cherry, D. S., Currie, R. J., Latimer, H. A., Cairns, J. Jr., Diz, R. B., Johnson, D.

M., and Yeager, M. M., 1999. Leading Creek Improvement Plan: Final Report to

Southern Ohio Coal Company (S.O.C.C.O.) and American Electric Power

(A.E.P.), Columbus, Ohio: Unpublished, 1 – 1 to 16 – 6.

9. Childress, C. J. O. and Jones, R. L., 1983. Sediment and Water Quality Data for

the West Branch and East Branch Shade River Basins, Ohio. U.S Geological

Survey Open – File Report 85 – 187.

10. Clean Water Act (CWA), 1972. Assessed at:

http://www.swrcb.ca.gov/laws_regulations/docs/fedwaterpollutioncontrolact.pdf

11. Conrey, G. W., Paschal, A. H., and Burrage, E. M., 1934. A Key to the Soils of

Ohio: Ohio Agricultural Experiment Station, Special Circular No. 44, 3 p.

12. Cross, W. P. and Hedges, R. E., 1959. Flow Duration of Ohio Streams: State of

Ohio, Dept. of Natural Resources, Division of Water, Bulletin 31, Report 3: 4 –

60.

13. Delbeek, C. J., and Sprung, J., 2005. The Reef Aquarium: Science, Art and

Technology. Two Little Fishies, Inc., 176 pp.

14. DeNicola, D. M., and Stapleton, M. G., 2002. Impact of Acid Mine Drainage on

Benthic Communities in Streams: The Relative Roles of Substratum vs Aqueous

Effects, Environmental Pollution 119, 310 pp.

15. Dickman, I. I., 1964. The Strip–Mine Reclamation Program in Ohio: The Ohio

Journal of Science 64 (2), 165 pp.

207

16. DeShon, J. E., 1995. Development and Application of the Invertebrate

Community Index (ICI), 15, in W.S. Davis and T. Simon (eds.). Biological

Assessment and Criteria: Tools for Water Resource Planning and Decision-

Making. Lewis Publishers, Boca Raton, FL: 217 – 243.

17. Deutsch, W. J., 1997. Groundwater Geochemistry. Fundamentals and

Applications to Contamination. New York: Lewis Publishers, 221 pp.

18. Drewes, H. G., 1984. Factors Affecting Water Quality and Macroinvertebrate

Distribution within a Small Black Hills Stream. M.S. Thesis 2573 South Dakota

State University (Unpublished).

19. Dufour, K., Meehan, M., Kley, A. V., Weber, B., Will, R., and Yeo, I., 2001.

Development and Change in the Big Darby Watershed: City and Regional

Planning Studio, Ohio State University. Assessed at http://facweb.knowlton.ohio-

state.edu/sgordon/research/darby/BigDarbyReport.pdf

20. Eby, N., G., 2004. Principles of Environmental Geochemistry. Brooke/Cole, Inc.,

330 pp.

21. Friel, E. A., Ehlke, T. A., Hobba, W. A., Ward, S. M. Jr., and Shultz, R. A., 1987.

Hydrology of Area 8, Eastern Coal Province, West Virginia and Ohio. US

Geological Survey Water Resources Investigations Open File Report 84 – 463, 16

pp.

22. Federal Water Pollution Control Administration (FWPCA), 1968. Stream

Pollution by Coal Mine Drainage, Upper Ohio River Basin. U.S. Federal Water

Pollution Control Administration, Wheeling, WV, 110 pp.

208

23. Gibbs, R. J., 1970. Mechanisms controlling world water chemistry. Science, New

Series, 170: 1088 – 1090.

24. Gilmore, G. and Bottrell, G. D., 1999. Soil Survey of Meigs County, Ohio. United

States Department of Agriculture, Natural Resources Conservation Service.

Columbus, Ohio.

25. Gleick, P. H., and Adams, D. B., 2000. The Report of Water Sector Assessment

Team of the National Assessment of the Potential Consequences of Climate

Variability and Change (For the U.S. Global Change Research Program). Pacific

Institute for Studies in Development, Environment, and Security, CA. Assessed at

http://www.gcrio.org/NationalAssessment/water/water.pdf

26. Goldin, A., 1987. Reassessing the use of loss-on-ignition for estimating organic

matter content in noncalcerous soils. Commun. Soil Sci. Plant Anal., 18: 1111 –

1116.

27. HACH, 2005. Water Analysis Handbook, HACH Headquarters, Loveland, CO,

4th Edition: 31 – 200.

28. Henriksen, A., Kamari, J., Posch and Wilander, A., 1992. Critical loads of acidity:

Nordic surface waters. Ambio., 21: 356 – 63.

29. Henrot, J. and Weider, R. K., 1990. Process of Iron and Manganese Retention in

Laboratory Peat Microcosms Subjected to Acid Mine Drainage, J. Envir. Qual.

19: 312 – 320.

30. Huizenga, J., 2004. Natural and Anthropogenic Influences on Water Quality: An

Example from Rivers Draining the Johannesburg Granite Dome. MS Thesis Rank

Afrikaans University MS (unpublished)

209

31. Kaplan, D. H., Bender, C., Kigochie, P., and Pleasant, J., 2001. The State of Ohio’

Urban Environment: Geographic Patterns and Recent Trends. Ohio Journal of

Science 101 (5): 79-89.

32. Karr, J. R., Fausch, K. D., Angermeier, P. L., Yant, P. R., and Schlosser, I. J.,

1986. Assessing Biological Integrity in Running Waters, A Method and Its

Rationale, Illinois Natural History Survey, Champaign, IL, Special Publication 5.

33. Krumgalz, B. S., Fainshtein, G., Gorfunkel, L and Nathan, Y., 1990. Fluorite in

Recent Sediments as a Trap of Trace Metal Contaminants in an Estuarine

Environment. Estuarine, Coastal and Shelf Sci., 30: 1 – 15.

34. Larimore, R. W., 1974. Stream Drift as an Indication of Water Quality:

Transitions of the American Fisheries Society 110: 627 – 637.

35. Lehane, B. M., Giller, P. S., O’Halloran, J., and Walsh, P. M., 2004. Relative

Influences of Catchment Geology, Land use and In-stream Habitat on Brown

Trout Populations in South-Western Ireland. Biology and Environment:

Proceedings of the Royal Irish Academy, vol 104B, No. 1: 43 – 54.

36. Madhavan, N., 2001. Environmental Chemistry of Fluoride Rich Groundwater

and Associated Soils in Ajmer District, Rajasthan, India. School of Environmental

Sciences, J.N.U., India Ph D (Dissertation).

37. National Environmental Protection Act (NEPA), 1969. Assessed at:

http://welcome.warnercnr.colostate.edu/class_info/nr420noon/nepa1969.pdf

38. Ohio Department of Agriculture, 2001. Quick Facts from Ohio’s Agricultural

Industry. Assessed at: http://www.state.oh.us/agr/quickag.htm

210

39. Panigrahy, B. K., and Raymahashay, B. C., 2005. River Water Quality in

Weathered Limestone: A Case Study in Upper Mahanadi Basin, India. J. Earth

System Science, 114: 533 – 543.

40. Pepper, I. I., Gerba, C. P., and Brusseau, L. M., 1996. Pollution Science:

Academic Press Ltd, San Diego, California. 1st Edition: 118 – 133.

41. Pond, G. J, 2004. Effects of Surface Mining and Residential Land Use on the

Headwater Stream Biotic Integrity in the Eastern Kentucky Coalfield Region:

Kentucky Department for Environmental Protection, Water Division: 5 – 14.

42. Post, J. E., 1999. Manganese Oxide Minerals: Crystal Structure and Economic

and Environmental Significance. Proc. National Academy of Science USA, 96:

3447 – 3454.

43. Rankin, E. T., Yoder, C. O., and Mishne, D., 1996. Ohio Water Resource

Inventory, Volume 1: Summary, Status, and Trends, Ohio EPA, Division of

Surface Water Monitoring and Assessment Section, Columbus, Ohio.

44. Robson, A. J., and Neal, C., 1997. A summary of Regional Water Quality for

Eastern UK Rivers, Science of the Total Environment, 194/195: 15 – 37.

45. Rodriguez, E., Sultan, R., and Hilliker, A., 2004. Negative Effects of Agriculture

on Our Environment. The Traprock, 3: 28 – 32.

46. Rose, A. W., Means, B., and Shah, P. J., 2003. Methods for Passive Removal of

Manganese from Acid Mine Drainage. West Virginia Surface Mine Drainage

Task Force Symposium, 73 p. Assessed at http://www.wvmdtaskforce.com

211

47. Sayler, 2006. Contemporary Land Cover Change in the North Central

Appalachians Ecoregion. Assessed at: http://edc2.usgs.gov/LT/regions/eco62.php

48. Science To Achieve Results (STAR, 2006). Biological Monitoring Plan for Fish,

Macroinvertebrates, Algae, Habitat, Water Chemistry, Hydrology, and

Geomorphology Sampling During Summer 2006 for Ohio University STAR

Grant. Athens, Ohio.

49. Soil and Plant Council, 1992. Handbook on Reference Methods for Soil Analysis,

Athens, GA, U.S.A.

50. Sparling, D. W., and Lowe, T. P., 1996. Reviews of Environmental

Contamination and Toxicity, 145. Springer-Verlag, New York.

51. Stevenson, R. J., and Lowe, R. L., 1986. Sampling and Interpretation of Algal

Patterns for Water Quality Assessments. In B.G. Isom (editor). Rationale for

sampling and interpretation of ecological data in the assessment of freshwater

ecosystems. ASTM STP 894. American Society for Testing and Materials,

Philadelphia, Pennsylvania. 118 – 149.

52. Stevenson, R. J., and Pan, Y., 1999. Assessing Ecological Conditions in Rivers

and Streams with Diatoms. In E.F. Stoermer and J.P. Smol (editors). The diatoms:

Applications to the Environmental and Earth Sciences. Cambridge University

Press, Cambridge, UK. 11– 40.

53. Stoertz, M., W., Bourne, H., Knotts, C., and White, M. W., 2002. The Effects of

Isolation and Acid Mine Drainage on Fish and Macroinvertebrate Communities of

Monday Creek, Ohio. Mine Water and the Environment, 21: 60 – 72.

212

54. Sturgeon, M. T., and Associates, 1958. The Geology and Mineral Resources of

Athens County, Ohio. Ohio Geol. Survey Bull. 57, 600 pp.

55. Sunday Creek Watershed Group, March 2003. A Comprehensive Watershed

Management Plan for the Sunday Creek Watershed. Glouster, Ohio. Assessed at

http://www.sundaycreek.org/images/sunday_mgmt032403.pdf

56. Surface Mining Control and Reclamation Act (SMCRA), 1977. Assessed at:

http://www.osmre.gov/smcra.htm

57. Swan, A. R. H., and Sandilands, M., 1995. Introduction to Geological Data

Analysis: New York, NY, Blackwell Science, 446 pp.

58. Tukura, B. W., Kagbu, J. A., and Gimba, C. E., 2007. Effects of pH and Total

Organic Carbon (TOC) on the Distribution of Trace Metals in Kubanni Dam

Sediments, Zaria, Nigeria: Science World Journal, 2: 1 – 6.

59. US Environmental Protection Agency, 1976. Quality Criteria for Water: Office of

Water Planning and Standards, United States Environmental Protection Agency,

Washington, DC. Pub. No. EPA 440/9-76-023.

60. U.S. Environmental Protection Agency, 1986. Quality Criteria for Water. Pub.

No. EPA 440/5-86-001

61. US Environmental Protection Agency, 1996. Acid Digestion of Sediments,

Sludges, and Soils - Method 3050B: “Test Methods for Evaluating Solid Waste,

Physical and Chemical Methods”, EPA Publication SW-846, 3rd Edition: 1 – 11.

213

62. US Environmental Protection Agency, 1997. Managing Non-point Source

Pollution from Agriculture. Pub No. 6. EPA841-F-96-004F.

63. Wang, X., 2001. Integrating Water Quality Management and Land–Use Planning

in a Watershed Context: Journal of Environmental Management 61: 25 – 36.

64. Wang, X., 2003, Urbanization and Environment: A Comparative Study of U.S.

and China. Assessed at:

(http://info.worldbank.org/etools/docs/library/37075/UP_Reading_Wang%20Xin

hao.doc)

65. Wyrick, G. G., and Borchers, J. W., 1981. Hydrologic Effects of Stress-Relief

Fracturing in an Appalachian Valley, U.S. Geological Survey Water-supply paper

2177, 51 pp.

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APPENDIX A: DESCRIPTIVE STATISTICS OF OTHER ELEMENTS IN THE

WATER AND SEDIMENT SAMPLES

A.1. Barium

The concentration of barium within WAP ranged from 0.10 mg/L at sites 51 and 70 to 0.38 mg/L at site 35; with a mean concentration of

0.21 mg/L and a standard deviation of 0.05.

Barium concentration within the Shade River Watershed varied from 0.15 mg/L at sites 23 and 39 to 0.38 mg/L at site 35; with a calculated mean concentration of 0.22 mg/L and a standard deviation of

0.05.

A.2. Strontium

Apart from iron, strontium had a relatively high concentration as compared to the other trace elements within the Shade River Watershed.

Strontium concentration within the WAP ranged from 0.06 mg/L at site 44 to 3.57 mg/L at site 14; with a mean concentration of 0.50 and a standard deviation of 0.50.

The concentration of strontium in the Shade River Watershed varied from 0.34 to 0.87 mg/L; with a calculated mean of 0.50 mg/L and a standard deviation of 0.12. The highest concentration was measured at site 41 while the lowest concentration was measured at sites 35 and 40.

215

A.3. Silica

Silica concentration within the WAP ranged from 0.1 mg/L at site

27 to 20.2 mg/L at site 44; with a mean concentration of 3.5 mg/L and a standard deviation of 2.2.

The concentration of silica within the Shade River Watershed ranged from 0.1 to 4.4 mg/L.The highest concentration was measured at

STAR site 36 and 42 while the lowest concentration was measured at site 26. The measured mean for the concentration was 2.8 mg/L and the standard deviation was 1.2.

A.4. Ammonia

Ammonia is an important nutrient for aquatic organisms. The main sources of ammonia in streams include agricultural runoff, untreated household or industrial waste, and bacterial decomposition of animal wastes. High level of ammonia is toxic to fish and exposure to slightly elevated levels can cause reduction in growth rate.

Ammonia as nitrogen concentration within the Shade River

Watershed was very low ranging from 0.03 mg/L at sites 34 and 43 to

0.35 mg/L at site 30; with an average concentration of 0.1 mg/L and a standard deviation of 0.10. The values measured for ammonia were far below the USEPA criteria for aquatic life (2.2 mg/L).

216

A.5. Lithium

The concentration of lithium in the sediments within the WAP ranged from 15 mg/Kg at site 44 to 347 mg/Kg at site 74; with a mean concentration of 121.6 mg/Kg and a standard deviation of 53.1.

Lithium sediment concentration within Shade River Watershed ranged from 82 mg/Kg at site 39 to 205 mg/Kg at site 31; with a mean concentration of 147 mg/Kg and a standard deviation of 39.

A.6. Cobalt

The concentration of cobalt in sediments within the WAP ranged from 6 mg/Kg at site 44 to 95 mg/Kg at site 73; with a mean concentration of 32 mg/Kg and a standard deviation of 16.

The concentration of cobalt in sediments within Shade River

Watershed ranged from 14 mg/Kg at site 28 to 79 mg/Kg at site 43; with a mean concentration of 30 mg/Kg and a standard deviation of 14.

A.7. Chromium

The concentration of chromium in sediments within the WAP ranged from 3 mg/Kg at site 76 to 59 mg/Kg at site 74; with a mean concentration of 22 mg/Kg and a standard deviation of 10.

217

The concentration of chromium in sediments within Shade River ranged from 10 mg/Kg at site 22 to 33 mg/Kg at site 34; with a mean concentration of 21 mg/Kg and a standard deviation of 7.

A.8. Copper

The concentration of copper in sediments within the WAP ranged from 6 mg/Kg at site 21 to 172 mg/Kg at site 73; with a mean concentration of 36 mg/Kg and a standard deviation of 21.

Copper concentration of sediments taken within Shade River ranged from 15 mg/Kg at site 26 to 59 mg/Kg at site 30; with a mean concentration of 37 mg/Kg and a standard deviation of 12.

A.9. Nickel

Nickel concentration in sediments taken within the WAP ranged from 9 mg/Kg at site 44 to 153 mg/Kg at site 74; with a mean concentration of 30 mg/Kg and a standard deviation of 22.

The concentration of nickel within sediments in the Shade River

Watershed ranged from 12 mg/Kg at site 33 to 90 mg/Kg at site 43; with a mean concentration of 34 mg/Kg and a standard deviation of 18.

218

A.10. Strontium

The concentration of strontium within sediments in the WAP ranged from 6 mg/Kg at site 72 to 220 mg/Kg at site 79; with a mean concentration of 38 mg/Kg and a standard deviation of 38.

The concentration of strontium in sediments within the Shade

River Watershed ranged from 11 mg/Kg at site 33 to 152 mg/Kg at site

30; with a mean concentration of 41 mg/Kg and a standard deviation of

34.

A.11. Zinc

Zinc concentration in sediments within the WAP ranged from 27 mg/Kg at site 9 to 6428 mg/Kg at site 78; with a mean concentration of

413.1 mg/Kg and a standard deviation of 733.5.

The concentration of zinc in sediments within Shade River

Watershed ranged from 36 mg/Kg at site 38 to 199 mg/Kg at site 38; with a mean concentration of 76 mg/Kg and a standard deviation of 41.

219

APPENDIX B

Figure B.1. Set up for the equipment used for vacuum filtration (filtered water samples).

Figure B.2. Set up for the equipment used for vacuum filtration (filtered water samples)

220

Figure B.3. Raccoon Creek (STAR Site 6) showing fish species in clean water with evidence of calcite precipitation.

Figure B.4. Huff Run (STAR Site 9) showing the precipitation of iron and manganese oxides. This is a typical AMD site.

221

Figure B.5. Goose Creek (STAR Site 11) located near a cattle ranch.

Figure B.6. Downstream (left) with no flow condition and upstream (right, with Josh Coe and Ashley Campbell) with low flow situated at Elk Fork (STAR Site 7)

222

Figure B.7. Shannon Cook (left) and Prosper Gbolo (right) measuring the flow of the stream and the chemistry of the stream respectively.

Figure B.8. Wakatomika Creek (STAR Site 21) showing clean surface water with significant amount of flow.