MINERALOGY AND PROVENANCE OF PINK INCLUSIONS IN THE ILLINOIAN

TITUSVILLE TILL, MAHONING COUNTY, EASTERN OHIO

A Thesis

Presented to

The Graduate Faculty of The University of Akron

In Partial Fulfillment

of the Requirements for the Degree

Master of Science

Belinda J. Franko

August, 2008 MINERALOGY AND PROVENANCE OF PINK INCLUSIONS IN THE ILLINOIAN

TITUSVILLE TILL, MAHONING COUNTY, EASTERN OHIO

Belinda J. Franko

Thesis

Approved: Accepted

Advisor Dean of the College Dr. John P. Szabo Dr. Ronald F. Levant

Faculty Reader Dean of the Graduate School Dr. LaVerne Friberg Dr. George R. Newkome

Faculty Reader Date Dr. John A. Peck

Department Chair Dr. John P. Szabo

ii ABSTRACT

Researchers, who have mapped glacial sediments within the glaciated

portion of the Allegheny Plateau, have noted the occurrence of isolated diamicts

having a pink coloring and containing more carbonate minerals than their

surrounding gray diamicts. Within a large continuous exposure in a strip mine

near North Lima, Mahoning County, Ohio, pink layers of diamict tend to thicken,

thin and bifurcate and may also surround clasts. Pink layers range from a few mm to approximately 80 cm in thickness and extend for more than 20 m laterally.

The texture, carbonate and clay mineralogy, and elemental composition of samples of pink and gray diamicts were examined for major differences. More

variation was found in the sand fractions of gray samples than in those of pink

samples. Pink samples average 31% sand, 43% silt, and 26% clay, whereas

gray samples contain 55% sand, 27% silt, and 18% clay; differences are

statistically significant at P ≤ 0.05. Pink diamicts have more total carbonate (% <

0.074 mm) in the medium-sand to silt fractions but contain 6.6% total carbonate

compared to 5.2% for gray diamicts. Within 1 – 2 mm fractions observable pink

sand grains were seen in pink samples but were not evident in gray samples.

Diffraction intensity ratios (DI) average 1.1 for pink diamict and 0.9 for gray

diamicts; this difference is also statistically significant. A 32-element chemical

analysis of both the sand and fine fractions shows that composition of pink

iii diamicts differs significantly from that of gray diamicts in 7 of 25 comparisons for the sand fractions and 12 of 25 for the fine fractions. Both sand and fine fractions contained significantly different amounts of Al, Ba, K, Mg, and V.

Geometry and laboratory analyses of diamicts at this site suggest that pink diamicts have a source in the Queenston and Grimsby formations of the Niagara

Peninsula. Eroded blocks of these formations may have been transported englacially and smeared out along shear planes in thrust-stacked gray units in the terminus of the Illinoian Titusville ice.

iv ACKNOWLEDGEMENTS

I would like to thank Dr. J. P. Szabo for all of his time, support and patience in helping me through this project. Next thanks to my committee for being there and answering questions when I knocked on their doors and for editing and presentation tips. I would also like to thank Mike Bohan and Tim

Miller at East Fairfield Coal Company for their time and help whenever needed. I also need to thank Tammy Richards, Tom Quick and Elaine Butcher without whom I would never have finished. Caitlin Nay gets special thanks for helping in the lab and being gentle with the old folk at Field Camp. And of course my family receives a big THANKS, my sons, Michael and Kyle for not complaining when dinner never appeared on a regular basis, my husband Mike for all for his special love and care, financial backing, and most of all support, despite himself.

v TABLE OF CONTENTS

Page

LIST OF TABLES ...... viii

LIST OF FIGURES ...... xii

LIST OF PLATES ...... xiv

CHAPTER

I. INTRODUCTION...... 1

II. GEOLOGY OF STUDY AREA ...... 7

Physiography ...... 7

Bedrock ...... 12

Glacial Geology ...... 14

Till Stratigraphy ...... 18

Glacial Processes ...... 20

III. METHODS ...... 24

Field Methods ...... 24

Laboratory Methods – Textural Analyses ...... 29

Laboratory Methods – Carbonate Analyses ...... 29

Laboratory Methods – X-ray Diffraction Analyses ...... 31

Laboratory Methods – Coarse-Sand Lithology Analyses ...... 32

Laboratory Methods – Chemical Analyses ...... 32

Laboratory Methods – Statistical Analyses ...... 32 vi IV. RESULTS ...... 34

General Observations ...... 34

Vertical Section Description ...... 38

Textural Analysis ...... 40

Carbonate Analysis ...... 40

Clay Mineralogy ...... 43

Coarse-Sand Lithology Analysis ...... 46

Chemical Analysis ...... 46

V. DISCUSSION ...... 52

Source Area ...... 99

Mechanism of Placement ...... 103

VI. CONCLUSION ...... 107

REFERENCES CITED ...... 109

APPENDICES ...... 113

APPENDIX A. FIELD DESCRIPTIONS OF SAMPLES ...... 114

APPENDIX B. DATA FROM TEXTURAL ANALYSIS OF ALL SAMPLES ...... 117

APPENDIX C. DATA FOR CARBONATE ANALYSIS DATA OF SAND, SILT, AND SILT AND CLAY FRACTIONS ...... 119

APPENDIX D. CRYSTALLINE AND CLASTIC DATA ...... 122

APPENDIX E. CHEMICAL ANALYSES OF SAND FRACTION ...... 124

APPENDIX F. CHEMICAL ANALYSES OF SILT AND CLAY AND SOURCE ROCKS ...... 128

vii LIST OF TABLES

Table Page

1. Descriptive statistics for textural analysis by color...... 41

2. Descriptive statistics for carbonate analysis by color and size fraction .. 42

3. Descriptive statistics for carbonate analysis of sand fractions...... 44

4. Descriptive statistics for coarse-sand lithology and DI’s of glycolated samples...... 45

5. Descriptive statistics for chemical analysis (ppm) of sand fractions ...... 48

6. Descriptive statistics for chemical analyses (ppm) of silt and clay fraction ...... 49

7. Results of chemical analyses (ppm) of suspected source rock ...... 51

8. F tests comparing variances in size fractions between different groups (+ signifies significant difference at P ≤ 0.05). g = gray, p = pink, b = brown, pb = pink-brown ...... 53

9. Groups having the larger variances in size fractions when comparing various combinations of groups (+ signifies the high variance by color) ...... 54

10. Results of t tests comparing means of all size fractions between different combinations of groups (+ signify significant difference at P ≤ 0.05) ...... 56

11. Groups having the larger means when comparing textural parameters using various combinations of groups (+ signifies the high variance by color)...... 57

12. F tests comparing variances in carbonate contents of the sand fractions between different groups (+ signifies significant difference at P ≤ 0.05)...... 59

viii 13. F tests comparing variances in carbonate contents of the silt and clay fractions (% < 0.74 mm) (+ signifies significant difference) ...... 60

14. F tests comparing variances in carbonate content of the silt fraction (+ signify significant difference at P ≤ 0.05) ...... 61

15. Groups having the larger variances in carbonate content when comparing various combinations of groups in various sand fractions (+ signify the high variance by color) ...... 63

16. Groups having the larger variances in carbonate content of the < 0.074 mm fraction when comparing various combinations of groups (+ signifies the high variance by color) ...... 64

17. Groups having the larger variances in carbonate content in silt fractions when comparing various combinations of groups (+ signify the high variance by color) ...... 65

18. T tests comparing means in carbonate content of the sand fractions (+ signifies significant difference at P ≤ 0.05) ...... 66

19. T tests comparing means in carbonate contents of the < 0.074 mm fractions (+ signifies significant difference at P ≤ 0.05) ...... 67

20. T tests comparing means in carbonate content of the silt fractions (+ signifies significant difference at P≤ 0.05) ...... 68

21. Groups having the larger means when comparing carbonate contents of sand fractions of various combinations of groups (+ signifies the high variance by color) ...... 69

22. Groups having the larger means when comparing carbonate contents of the < 0.074 of various combinations of groups (+ signify the high variance by color) ...... 71

23. Groups having the larger means when comparing the silt fractions of various combinations (+ signifies the high variance by color) ...... 72

24. F tests comparing variances in coarse sand lithologies and DIs between groups (+ signifies significant difference) ...... 73

25. Groups having the larger variances when comparing various combinations of groups within the coarse-sand lithologies and DIs (+ signifies the high variance by color) ...... 74

ix 26. T tests comparing means in coarse sand lithologies and DIs (+ signifies significant difference) ...... 75

27. Group having the larger means in the coarse-sand lithologies and DI when comparing various combinations of groups (+ signifies the high mean by color) ...... 76

28. F tests comparing variances in chemical analyses of sand fractions (+ signifies significant difference) ...... 78

29. Group having the larger variances when comparing chemical analyses of various combinations of groups within the sand fractions (+ signifies the high variance by color) ...... 79

30. F tests comparing variances in chemical analyses of silt and clay fractions (+ signifies significant difference) ...... 80

31. Groups having the larger variances when comparing chemical analyses of various combinations of groups within the silt and clay fractions (+ signifies the high variance by color) ...... 81

32. T tests comparing means of chemical analyses of sand fractions (+ signifies significant difference) ...... 82

33. Groups having the larger means when comparing chemical analyses of various combinations of groups within sand fractions (+ signifies the high variance by color) ...... 83

34. T Tests comparing means in chemical analyses of silt and clay fractions (+ signifies significant difference) ...... 84

35. Groups having the larger means for chemical analyses when comparing various combinations of groups within the silt and clay fractions (+ signifies the high variance by color) ...... 85

36. F tests comparing variances in chemical analyses between size fractions within each color group (+ signifies significant difference) ...... 87

37. Size fractions having the larger variances when comparing chemical analyses of size fractions within the same color (+ signifies the high variance by color) ...... 88

38. T tests comparing means for chemical analyses of size fractions within the same color (+ signifies significant difference) ...... 89

x

39. Groups having the larger means for chemical analyses when comparing size fractions within the same color (+ signifies the high means by color)...... 90

40. Correlation matrix for elemental comparisons in the sand fractions ...... 91

41. Correlation matrix for elemental comparisons in the silt and clay fractions ...... 94

42. Comparisons of elemental compositions of source rocks to those of size fraction of diamicts of various colors. Numbers are percent differences. (BD = delow detection) ...... 96

xi LIST OF FIGURES

Figure Page

1. Lobe map of northeastern Ohio (modified from White, 1971) ...... 2

2. First exposed high wall in the East Fairfield Coal Co. mine in North Lima Mahoning County, Ohio. Maximum height of the high wall is 10 m ...... 3

3. Relationship of pink layers. a.) Weathered gray diamict with pink inclusions. Marker is 13.5 cm long. b.) Gray diamict with pink wrapping around a clast. Each block of the scale equals 1 cm...... 5

4. Glacial lobe map of the southern margin of the Laurentide ice sheet (modified from Mickelson and others, 1983) ...... 8

5. Physiographic provinces of Ohio (modified from Brockman, 1999)...... 9

6. Major watersheds within Mahoning County area (modified from: http://www.watershed.cboss.com/images/mwatshdcol.jpg). The study area is within the North Fork Little Beaver Creek basin in the southeast part of the county...... 11

7. Bedrock map of northeastern Ohio (modified from Slucher and others, 2006) ...... 13

8. Glacial map of the study area showing distribution of Wisconsinan deposits. Wkg = Kent ground moraine; Wke = Kent end moraine; Wle = Lavery end moraine; Wlg = Lavery ground moraine; Wl = lake bed; Wo = outwash; Wk = kames and kame terraces...... 17

9. Field occurrence of the pink diamict found in study area. a.) Relationship of the gray, brown and pink diamict, scale marked in cm. b.) fine channel sand occurs between layers of diamict. c.) Pink outlined layer within the gray diamict ...... 26

xii 10. The procedure used to collect samples for the vertical section. a.) Section begins at the bedrock. b.) Sampling along a horizontal pink layer in the high wall ...... 27

11. Sample locations on north face of surface mine ...... 28

12. Weathered gray (brown) is found on newly opened section of the high wall. a.) Removal of blocky weathered diamict. b.) Close up of weathered till with pink layer...... 30

13. Pink layers wrap around clasts. a.) Pink wrapping around large limestone clasts. b.) Pink wrapping around small clasts...... 35

14. Relationship of pink diamict in the gray and brown diamict. a.) Sand layer between layers of diamict. b.) Contact between gray and weathered diamict. c.) Peat balls below a pink layer ...... 36

15. Deformation of tills. a.) Folding of till; section is 10 m high. b.) Layering with some deformation; section is 5 m high...... 38

16. Trilinear plot of textural data (+ = gray diamict, ●= pink diamict, red symbol = mean) ...... 58

17. Diagram representing thrust stacking (modified from http://www.geus.dk/publications/bull/nr8/nr8_p148-192-dk.htm ...... 105

xiii

LIST OF PLATES

Plate 1. Laboratory Analysis of Vertical Section

xiv CHAPTER I

INTRODUCTION

This study was proposed by Dr. Gary Fleeger of the Pennsylvania

Geological Survey after viewing exposures of Titusville Till containing pink inclusions in a strip mine of the Pennsylvanian Vanport Limestone owned by the

East Fairfield Coal Co. near North Lima, Ohio (Figure 1). Dr. Fleeger contacted

Dr. Szabo of the Department of Geology and Environmental Science (June,

2005) at The University of Akron regarding the origin and composition of the pink

inclusions. Some photos (Figure 2) were sent along with preliminary samples to

the Department.

Preliminary analysis of the samples suggested that the pink inclusions

contain more fine carbonates (% < 0.074mm) than the surrounding gray diamicts.

These pink inclusions in the Titusville Till have been recognized throughout much

of northeastern Ohio (White, 1982) and northwestern Pennsylvania (White, and

others, 1969). Similar inclusions have been investigated in northeastern Illinois

in the Tiskwilwa Till (Johnson and others, 1985). No one has investigated the

differences between these pink inclusions and their associated gray diamicts or

the mode of origin of the pink inclusions in northeastern Ohio.

1 Figure 1. Lobe map of northeastern Ohio (modified from White, 1971). Figure 1. Lobe map of northeastern

2 Mahoning County, Ohio. Co. mine in North Lima East East First exposed high wall in the East Fairfield Coal

Maximum height of the high wall is 10 m. West Figure 2. 3 Strip pits in the North Lima, Ohio, surface mine from where the samples

were collected display pink inclusions in layers that thicken, thin and bifurcate

(Figure 3a). The pink coloration also wraps around clasts within the layer (Figure

3b). These layers of pink sediment can have either a sharp contact or can occur

as irregular-shaped, different-sized blebs along a diffuse contact with the gray

sediments. Pink layers are also found in gray sediments that have been

weathered to grayish brown or brown (Figure 3a). Pink layers are not only more

calcareous than the surrounding gray sediments, but also appear to be more clay rich.

Location

The study site is a surface mine owned by East Fairfield Coal Co. located on the glaciated Allegheny Plateau near North Lima, Ohio, just southeast of

Youngstown in Mahoning County on the Ohio-Pennsylvania state line (Figure 1).

The company is mining Pennsylvanian-age Vanport Limestone overlain by assorted sediments including glacially tectonized limestone clasts, sand, diamicts, clays and silts (Totten and White, 1987). The mine (Figure 1) is located within the Wisconsinan Kent Moraine (White, 1982).

Objectives

The purpose of this research is to determine the origin of pink calcareous inclusions (Munsell Color of 2.5YR 4/2, weak red and 2.5YR 4/4, reddish brown) in the Titusville Till using both field evidence and laboratory analyses. I hypothesize that the origin of the inclusions may be caused by different

4

a.)

b.)

Figure 3. Relationship of pink layers. a.) Weathered gray diamict with pink inclusions. Marker is 13.5 cm long. b.) Gray diamict with pink wrapping around a clast. Each block of the scale equals 1 cm.

5 subglacial processes that have produced not only differences in coloration but also differences in texture and chemical composition. The pink inclusions have several possible sources. A large subcrop of older pink Keefus Till is found in

Ashtabula County (White and Totten, 1979) north of the site in Mahoning County.

Bruno (1988) thought that pink inclusions in the Late Wisconsinan Ashtabula Till originated from comminuted clasts of the Grimsby Formation (Lower Silurian

Medina Group, 443-428 Ma) of the Niagara Falls area. Another source may be the comminution of local limestone bedrock because pinkish diamicts in northeastern Ohio generally appear to be more calcareous in content (Szabo, personal communication).

6 CHAPTER II

GEOLOGY OF STUDY AREA

Deposits of two glaciations, the Illinoian and Wisconsinan stages, of the

late Pleistocene Epoch are pertinent to this study. These glaciations consist of

numerous ice advances and retreats during which many different tills were

deposited (Totten and White, 1987). Titusville Till is the till being studied in this paper and has had many ages assigned to it with the current thought being

Illinoian (Szabo, 1992; Szabo and Totten, 1995).

Physiography

During the late Pleistocene epoch, north-central and northeastern North

America was covered by the Laurentide ice sheet (Mickelson and others, 1983).

The flow of the ice sheet at its southern margin (Figure 4) was influenced by the pre-existing topography of the region that fragmented the margin into many sublobes with uphill flow taking place in the southern margin (Mickelson and others, 1983). Within Ohio the interaction of glaciers with pre-existing topography produced three physiographic provinces (Figure 5). The Central

Lowlands can be subdivided into The Huron-Erie Plains and Till Plains; whereas the Interior Low Plateau forms the Blue Grass section. The Appalachian

Plateaus consist of the Glaciated Allegheny Plateaus, and unglaciated Allegheny

7 8

Figure 4. Glacial lobe map of the southern margin of the Laurentide ice sheet (modified from Mickelson and others, 1983). INTERIOR LOW PLATEAU Bluegrass Section

Figure 5. Physiographic provinces of Ohio (modified from Brockman, 1999).

9 Plateaus (Brockman, 1999). The study area is within the Glaciated Allegheny

Plateaus; more specifically on a plateau referred to as the Killbuck-Glaciated

Pittsburgh Plateau, which stretches in a narrow band from Ross County north to

Richland County where it widens northeastward to the Portage escarpment and

eastward through Ashland, Holmes, Stark and Columbiana Counties into western

Pennsylvania. This area is characterized by ridges and flat uplands (Brockman,

1999) having discontinuous drift caused by successive glaciations removing

older unconsolidated deposits overlying resistant bedrock hills. The bedrock

surface topography suggests that before glaciation this area was maturely

dissected. Many of the buried valleys are as deep as 152 m and have been filled

with glacial sediments. Much of this area was covered by glacial drift; thus the modern topography appears to be in a late youthful stage (White, 1982). Glacial deposits may be as much as 61 m thick (White, 1982).

The current drainage patterns (Figure 6) have been greatly influenced by glaciation of Mahoning County. Previous glaciation has filled valleys, dammed rivers, and changed the flow of the drainage in the area. Originally the drainage of the area was to the north, but with the repeated oscillations of the ice front, drainage was diverted southward causing modern day rivers and streams to incise valleys, (Totten and White, 1987).

Drainage within Mahoning County is an intricate network of streams flowing in all directions. The majority of the county is contained within the Ohio River drainage basin, and most surface water reaches this river by way of the Mahoning River

(Totten and White, 1987). There is a rather erratic drainage pattern in this area

10

Figure 6. Major watersheds in Mahoning County area (modified from: http://www.watershed.cboss.com/images/mwatshdcol.jpg). The study area is within the North Fork Little Beaver Creek basin in the southeast part of the county.

11 having many streams initially flowing northward, but then reversing direction to flow south-southeast. Other streams flow directly eastward, whereas others flow south to enter the Ohio River drainage basin by way of Little Beaver Creek

(Totten and White, 1987). Many stream courses are controlled by resistant bedrock hills (Totten and White, 1987). The study area lies within the North Fork

Little Beaver Creek watershed (Figure 6) that drains southward through

Columbiana County entering the Ohio River just north of Liverpool, Ohio.

Bedrock

Generally, the bedrock of northeastern Ohio (Figure 7) consists of

Mississippian siltstones and sandstones overlain by Pennsylvanian conglomerates, sandstones, shales, limestone and coal (White, 1982). Along the

Lake Erie shoreline and within deeply-incised valleys, Devonian shale

(predominantly the Chagrin Shale member (White, 1982)) may crop out or underlie unconsolidated sediments in buried valleys.

Bedrock within Mahoning County also consists of Mississippian shales and sandstones, whereas the Pennsylvanian rocks consist not only of sandstones, but also limestones, clay and coal (Totten and White, 1987).

Because of the glacial cover, Mississippian bedrock crops out only in the northern-central section of the county and occurs in deeply incised valleys and along eroded hillsides near Youngstown (Totten and White, 1987).

12

Figure 7. Bedrock map of northeastern Ohio (modified from Slucher and others, 2006)

13 Pennsylvanian bedrock consists of the Pottsville and Allegheny groups. The

Pottsville Group is found in the northern and central section of the county and within deep valleys. The Allegheny Group is found in the southern part of the county and forms the surface bedrock of the central section of the county. These groups contain many thinly-bedded horizontal strata allowing for the mining of several resources at once (Totten and White, 1987). Coal of the Upper and

Lower Mercer (lower Pottsville Group) and the Vanport Limestone of the

Allegheny Group are both extracted from surface and underground mines (Brant,

1964).

Glacial Geology

Northeastern Ohio, northwestern Pennsylvania, and western New York were all glaciated by the Grand River sublobe of the Erie lobe from the

Laurentide Ice sheet (Figure 4). The Erie lobe was split by the unusually high subglacial topography of the Appalachian Plateau. These bedrock highs may have been nunataks, at the time of the maximum glaciation (Mickelson and others, 1983; Totten and White, 1987) causing the sublobes to develop. As ice flowed uphill onto the plateau, increased shearing processes in the area

(Mickelson and others, 1983) causing increased till thicknesses.

Surface features of Mahoning County were produced by glaciation. Ground moraine, end moraines, kames, kame terraces, valley trains and lake plains are all evident in this region (Totten and White, 1987). Ground moraine forms surfaces of gently rolling hills, sometimes reflecting underlying bedrock

14 topography. Ground moraine in the northern sections of Mahoning County

covers an expanse of 259 km2 and becomes flat enough to the west and north to

be called a till plain. Other ground moraine found in the remainder of Mahoning

County reflects underlying bedrock surfaces. Ground moraine consists of very

thin till sheets no more than 6 m thick in the north and ranges from 2 to 4 m in

thickness in other areas (Totten and White, 1987).

End Moraines are described as discontinuous hummocky hills formed

near the ice margins by oscillating ice fronts (Totten and White, 1987). The end

moraines in northeastern Ohio generally run in an east-west direction, but some bending does take place and defines the sublobes of the Erie Lobe (Goldthwait and others 1961). In Mahoning County, moraines are discontinuous and cannot be correlated with certainty to the moraines of the Killbuck lobe (Totten and

White, 1987). However; in southern Mahoning County an end moraine has been correlated with the Kent Moraine (White, 1982), and is divided into two sections: a continuous ridge in northern Columbiana County, and a discontinuous section of unconnected ridges in southern and central Mahoning County. These discontinuous moraine tracts tend to parallel the Kent and Titusville till boundaries (Totten and White, 1987).

Glaciofluvial landforms are also common within this area. Kames, kame terraces, and valley trains are all evident within Mahoning County. These features contain sands and gravels deposited through meltwater processes of

ablating glaciers. The streams originate below, within and on top of glaciers, and

15

may carry sediments beyond the glacial limits (Totten and White, 1987). Some

of the landforms created by older glaciations may be distorted by overriding ice

that changes their topographic expression making them difficult to identify.

Repeated glaciation has deposited several layers of till over these features and gives them a layered stratigraphy (Totten and White, 1987). Kame terraces were formed within the valleys as streams flowed around the stagnant ice, and may have been overridden by later ice advances, allowing additional till layers to cover the original landforms (Totten and White, 1987).

Most kames in the study area occur within valleys and are distinguished by flat or gradual sloping surfaces and steep sides (Totten and White, 1987;

Benn and Evans, 1998). Generally they have more consistent slope angles than those of hummocky moraine because of their internal structure and composition

(Benn and Evans, 1998). The kames and kame terraces in the study area are within Honey Creek Valley and have mostly been mined (Totten and White,

1987). The remaining remnants of a kame terrace in Honey Creek Valley begin near Middletown and continue southeastward into Pennsylvania (Totten and

White, 1987). Geomorphically the strip mine examined in the study area is within a kame terrace (Figure 8) that extends along Honey Creek Valley (Totten and

White, 1987).

Valley trains are formed as proglacial rivers transport and deposit a large sediment load. Deposition is caused by many variables including changes in channel gradient, large bedload, bed substrate, and variable water discharge.

These rivers tend to be braided (Benn and Evans, 1998). In addition to the kame

16

Figure 8. Glacial map of the study area showing distribution of Wisconsinan deposits. Wkg = Kent ground moraine; Wke = Kent end moraine; Wle = Lavery end moraine; Wlg = Lavery ground moraine; Wl = lake bed; Wo = outwash; Wk = kames and kame terraces.

17 terraces, the valley train (Figure 8) in the Honey Creek area, Mahoning County,

is approximately 1 km wide and 6 km long and extends southward into

Columbiana County (Totten and White, 1987).

Till Stratigraphy

Most tills within this region are a combination of pre-existing lake

sediments from the ancestral Lake Erie basin, local bedrock, and far-traveled

rock types. Many constituents are originally from Precambrian igneous and

metamorphic rocks of the Canadian Shield; and others are derived from

carbonate and fine-grained rocks of the Ordovician, Silurian, Devonian periods

(Mickelson and others, 1983).

Pre-Illinoian and Illinoian tills of the Grand River lobe consist of three till

units (Szabo, 1995). The oldest unit formed during a Pre-Illinoian glaciation is

the Slippery Rock Till (Volpi and Szabo, 1988). This is a deeply weathered till

(Totten and White, 1987) and has a paleosol developed in its upper surface

during some interglaciation. During the Illinoian stage the silty sandy Mapledale

Till (Volpi and Szabo, 1988; Totten and White, 1987) was deposited by the Grand

River lobe extending to Warren County, Pennsylvania. A thick paleosol may

have formed on the Mapledale Till during the Sangamonian interglaciation.

The Titusville Till was originally thought to be Middle Wisconsinan in age

but is now considered to be a product of an Illinoian glaciation (Szabo and

Totten, 1995). This olive brown till may consist of several layers. The Titusville

Till has been dated indirectly through the C14 dating process using peat found at

18 an elevation significantly below the till. The date of the peat was determined to

be about 40,000 B.P. (White and others, 1969) which was interpreted to mean

that the till was Altonian (“early” Wisconsinan) in age. White (1982) correlates the Titusville Till with the Mogadore Till of the Cuyahoga lobe and Millbrook Till of the Killbuck lobe in Ohio. Currently the Titusville Till has been assigned to the

Illinoian glaciation because the Titusville Till has never been found overlying the peat at its type section, nor do ice volume curves allow for glaciation as far south as Ohio and Pennsylvania during the early and middle Wisconsinan substages

(Szabo and Totten 1992; Szabo, 2006).

In the study area Titusville Till is considered a subsurface till and is overlain by Kent and Lavery tills of late Wisconsinan age and extends into northwestern Pennsylvania. The Titusville Till may be composed of three to five units (White and others, 1969). Titusville Till is predominately underlain by bedrock, but a few sites have older tills beneath it. Titusville Till is one of the thickest tills in this area and may be up to 6 m thick (White and others, 1969). Its

mean thickness is approximately 2.8 meters, and it contains extensive sand and

gravel lenses. Sands and gravels associated with the Titusville advance are strip

mined extensively (Totten and White 1987). The thickness of this till varies from

nonexistent to 10 m along the Titusville ice margin and was built by repeated

thrust stacking of ice as the ice front oscillated locally in eastern Ohio (Moran,

1967 and 1971). Titusville Till makes up the bulk of till within the Allegheny

Plateau and is described as being a hard, compact, stony, weakly calcareous,

19 gray diamict that oxidizes olive brown and fractures into blocks (Totten and

White, 1987).

Late Wisconsinan ice advances deposited at least three till units. The

Kent Till, the oldest Late Wisconsinan till is yellowish brown when oxidized, and has a sandy loam to fine sandy loam texture. The Kent Till can be distinguished from the younger Titusville Tills by its friable consistency. The thickness of Kent

Till and its associated outwash suggest that Kent ice may have remained in northeastern Ohio for several thousands of years before it retreated into Canada

(Szabo, 2006). The tills deposited after the Erie interstade are usually thin

(Mickelson and others, 1983). After the interstade, another ice advance deposited dark-brown, calcareous, silty clay, Lavery Till (Totten and White,

1987). After a brief retreat, another ice advance deposited the dark-brown, calcareous, clayey Hiram Till (Totten and White, 1987) having abundant black

Devonian shale clasts. The Ashtabula Till is the youngest glacial deposit in Ohio and its associated moraine is a complex of diamicts, outwash and lacustrine deposits (Bruno, 1988).

Glacial Processes

Many subglacial processes appear to be responsible for deposition of the

Titusville Till. Titusville Till may have been deposited by thrust stacking (Moran,

1967, 1971), deformation, lodgement, and melt-out processes (Szabo, 2006) caused by the oscillation of the ice of the Grand River lobe (Totten and White,

1987). These processes may account for the excessive thickness of till especially in valleys.

20 Three types of deformation have been identified: “simple in situ deformation,” “large-scale block inclusion,” and “transportational stacking within a single till sheet” (Moran, 1971). In situ deformation is formed through the ice pushing on soft basal till or bed shearing of the basal till (Whiteman, 1995).

Evidence consists of small simple folds in till, bedrock and stratified drift and minor displacements of faulted till. This type of deformation is found near the bedrock contact with the drift (Moran, 1971). These features tend to become homogenized with matrix material as shear strain increases (Van der Wateren,

1995). These shear strains tend to vary throughout the glacier having the highest rates in the center and decreasing to near zero at the margins of the ice sheet. Tills of this nature are found near the end of the glacial transport system

(Van der Wateren, 1995). This type of deformation has been noted by Moran

(1971) in the Titusville Till in a surface mine high wall in eastern Mahoning

County, Ohio, and at other locations north of the study area.

Large-scale block inclusions may include bedrock and large pieces of till that are transported from there original position. This type of deformation has also been noted by Moran (1971) and other works (Sardeson, 1905, 1906;

Bluemle, 1966; Brown, 1933; Lammerson and Dellwig, 1957; Dellwig and

Baldwin, 1965) in many locations and are recognizable by the fact that they may be underlain by younger till. Excessive pore-water pressure helps dislodge and move the masses above the younger till (Moran, 1971).

Transportational stacking within a single sheet (thrust stacking) is formed through the transport and deposition of glacial sediments (Moran, 1971). This

21 process can cause movement of older basal debris to a new site of deposition.

Thrust stacking is a subglacial process whereby the compressive flow at the edges of the glacier and up scarps causes shearing in the basal till. Most of the transport in this type of deformation takes place along shear planes where there is low shear strength in the basal till (Moran, 1971; Van der Wateren, 1995.

Thrust stacking is most easily identified by repetition of the depositional sequence and included blocks of bedrock or older till within the younger till.

Folds and faults may be recognizable within these sheets (Moran, 1971).

Feldspar content was used to determine these breaks in a sequence of Titusville

Till north of the study area, and it was originally thought that these till sheets represented multiple ice advances of an oscillating ice front (Moran, 1967).

Moran (1971) determined that the feldspar content breaks separate thrust planes and that repeated thrusting greatly increased the thickness of the Titusville Till near its ice margin.

Lodgement tills occur were basal debris is deposited onto the substrate by the basal pressure of the moving glacier (Whiteman, 1995). This process takes place when the flow force is not effective enough to overcome basal friction and continue to move basal debris (Drewery, 1986). Frictional force of the ice moves clasts within the soft impermeable layer of the till causing deformation. Because these sediments are at the basal layer of the glacier, continuous force is applied and will cause deformation of basal layer until the force is removed.

Melt water ever present at the base of a glacier, will also affect the overall characteristics of basal till and may even form a sorted or meltout till (Drewery,

22 1986). Meltout till is caused by the melting of ice in the debris-rich basal layer.

Basal sliding produces heat and allows the ice to melt leaving behind the debris.

This type of melting is proportional to the thickness of the ice; thin ice has less heat available and thicker ice has more available heat due to overburden

pressure (Drewery, 1986). Marginal ice will also conduct heat at a faster rate

due to ambient air temperature, precipitation and wind (Whiteman, 1995). During ablation of the ice, meltout may dominate, and higher heat is available causing thicker layers of till to be deposited (Whiteman, 1995). During glacial creep, melt out allows till deposition to take place at a slower rate (Drewery, 1986). Meltout over successive years may give the basal till a bedded appearance especially at layer boundaries where seasonal meltwater has removed fines (Drewery, 1986).

23 CHAPTER III

METHODS

Field Methods

Four trips were made to the site of the East Fairfield Coal Company surface mine near North Lima, Ohio. The first trip was taken in September 2006, during which, samples were taken starting in the northeast corner of an east-west trending high wall. Samples taken along the pink contact were described using color (Munsell color chart, 1954) and noting texture, structure, consistency and reaction with HCl. A starting point was determined in a pink layer along the wall at the northeast corner, and samples were taken moving westward. These samples (nos. 49-54, Figure 9a) were taken at 5-cm intervals following the pink layer for 25 cm; both the gray and pink diamicts were sampled along the contact.

The pink layer was followed for 3 m, and two more samples were taken at

contacts; a grab sample (no. 55) was taken at a point of interest (3 m west and

10 cm above the contact). Continuing westward three more samples were taken

(nos. 58-60, Figure 9b, c) at 5-cm intervals. Farther southeast along the wall samples (nos. 60-63) were retrieved. In this section a cycle was observed consisting of gray clay, red clay, and sand repeating itself vertically three times.

On a second trip a new pit had been opened, and sampling (nos. 1-18,

Figure 10a) began at the limestone bedrock. Samples were taken from the

24 bedrock surface at 25-cm intervals vertically up to 175 cm above the bedrock

(Figure 11). After that, samples were collected across the pink layers above the bedrock at 5-cm intervals to a height of 250 cm above rock, and then began horizontally (Figure 10b, 11) where the pink layer continued westward along the wall. Samples were taken at 25-cm intervals up to 125 cm from the vertical section where the pink layer appeared to pinch out. The pink layer reappeared at a distance of 250 cm and samples were taken at 250 and 275 cm from the vertical section. Samples (nos. 26-48) were also taken eastward (Figure 11) from the vertical section at 25-cm intervals to 325 cm where colluvium covered the pink layer. Sampling commenced horizontally 695 cm eastward of the vertical section, sample at 715 cm and 720 cm and continued at 10-cm intervals to 780 cm and then again at the 795 cm where the pink layer disappeared.

Additional observations were made in new trenches on the third and fourth trips during which large blocky layers of weathered brown and pink diamicts were found. During these trips, samples (Figure 12a, b) showing the relationship of weathered diamict to the pink layers were observed, and some additional samples were collected. A shale layer appeared above the limestone and sloped upwards to the east. The gray diamict containing a pink layer of diamict terminated against this rising shale knob.

25

a.) b.) c.)

26 Figure 9. Field occurrence of the pink diamict found in study area. a.) Relationship of the gray, brown and pink diamict, scale marked in cm. b.) Fine channel sand occurs between layers of diamict. c.) Pink outlined layer within the gray diamict.

a.)

b.)

Figure. 10. The procedure used to collect samples for the vertical section. a.) Section begins at the bedrock. b.) Sampling along a horizontal pink layer in the high wall.

27 West East 18 43 17 15, 16 46 41 45 25 24 23 22 21 20 19 26 27 28 29 3130 3332 3534 36 37 3938 gap 40 48 14 13 42 47 3 2 1 12 11 123 744 8 m 10 9 8

28 7 6 5 1 m 4 3 2 1 Vanport Limestone

sample location

Figure 11. Sample locations on north face of surface mine. Laboratory Methods – Textural Analyses

The matrix textures (% < 2 mm) of all samples were analyzed using

sieving and pipetting methods modified from Folk (1974). The samples were

thoroughly air dried, 50 g of each sample was put in a beaker with sodium

hexametaphosphate, and DI water was added as a dispersant for 24 hours.

Settling times for < 4 μ clay fraction were calculated for varying temperatures,

and at the appropriate time, 20 mL of the suspension was pipetted. The

remaining sample was washed through a 0.063-mm screen, dried, and separated

into sand fractions using sieves and a ro-tap. Percent clay and percent sand

were subtracted from 100 to calculate the percent silt in each sample.

Laboratory Methods - Carbonate Analyses

Calcite and dolomite percentages for the < 0.074-mm fraction (silt and clay

combined) of all samples were determined gasometrically using a Chittick

apparatus (Dreimanis, 1962). Samples were lightly ground in a mortar and

pestle and sieved through a 0.074 mm screen; 1.70 g of sieved sample were

placed in a flask with a magnetic stirrer and attached to the apparatus. Twenty

milliliters of 6 N HCl were delivered to the sealed flask, and pressure readings were taken upon completion of the HCl delivery and then again after 20 minutes.

Percentages of calcite and dolomite were determined after the readings were corrected to standard temperature and pressure.

29

a.)

b.)

Figure 12. Weathered gray (brown) is found on newly opened section of the high wall. a.) Removal of blocky weathered diamict. b.) Close up of weathered till with pink layer.

30 Carbonate contents of the silt fractions were determined using the Chittick

apparatus also. This fraction was separated from the clay fraction after

dispersion using a centrifuge having a speed of 1000 rpm for 1 minute 10

seconds. This fraction was dried and analyzed. The readings were again

corrected for standard temperature and pressure before calculating the calcite

and dolomite contents.

Carbonate contents of individual sand fractions were determined for all

samples. Each sample was weighed, placed in a small beaker, and enough 6 N

HCl was added to cover the samples. The samples were allowed to react

overnight, rinsed, dried, and reweighed. Percent carbonate was calculated from

the weight loss.

Laboratory Methods - X-ray Diffraction Analyses

Oriented mounts of clay minerals (< 2 μm) were prepared from slurry and allowed to air dry. All samples were x-rayed after glycolation; a few samples were analyzed under three other conditions: air dried, heated for 1 h at 450°C, and heated for 1 h at 550°C, to determine the type of chlorite in the sample and if kaolinite was present (Szabo and Fernandez, 1984; Volpi and Szabo, 1988). All samples were analyzed using Ni-filtered, Cu Kά radiation at 40 kV and 30 ma.

Samples were scanned at the rate of 2°2θ/min from 2°2θ to 35°2θ. Clay minerals were identified using the flow chart printed by the USGS (Starkey and others,

1984). Diffraction intensity ratios (DI’s) were calculated (Willman and others,

1966) by dividing the counts under the 1.0 nm illite peak by the counts under the

0.7 nm kaolinite and chlorite peak.

31 Laboratory Methods - Coarse-Sand Lithology Analyses

Very coarse-sand fractions (1.0 - 2.0 mm) are representative of pebble

lithologies in tills (Anderson, 1957) and were examined to determine a crystalline

to clastic ratio. Samples were wet sieved through 2.0 mm and 1.0 mm screens.

Samples were then immersed in alizarin red solution to help identify the

limestone. The lithology of approximately 300 grains of each sample was

determined using a binocular microscope.

Laboratory Methods - Chemical Analyses

Chemical analyses of the sand fraction and the combined clay and silt

fractions were analyzed because it was observed that the pink coloration was

residing in the sand fraction. The sand fraction was ground in a ball mill and sieved through a 0.074-mm screen. The clay and silt fraction was disaggregated with a mortar and pestle and also sieved through the 0.074-mm screen. The

samples were placed in small vials, weighed, and recorded. The samples were

sent to a commercial lab (SGS. Inc., Toronto, Canada) where a 4-acid (HCl,

HNO3, HF, and HClO4) digestion was done. A 32-element analysis of each

sample was done using an ICP-MS, and data were standardized to ppm to make

statistical analyses comparable.

Laboratory Methods - Statistical Analyses

Laboratory data was analyzed using Microsoft Excel to examine significant

differences between gray and pink diamicts. Descriptive statistics consisting of

means, variances, and standard deviations were calculated for all diamict

32 groupings. F tests for similarity of variances and t tests for equality of means were also performed using a level of significance, P ≤ 0.05. Coefficients of regression (r) were calculated to determine significant relationships among variables measured on gray and pink diamicts. Additionally, variations within a single pink layer were compared to those of all pink diamicts collected for this study.

33 CHAPTER IV

RESULTS

General observations

The lower three meters of the exposure at the North Lima, Ohio, surface

mine, displayed pink inclusions and layers that thicken, thin and bifurcate. Pink coloring wraps around clasts within the layer (Figure 13a and b), and layers of

pink sediments can have either sharp contacts or can be mottled along diffuse

contacts with gray sediments. Some of these gray sediments containing pink

layers have been weathered grayish brown to brown. Pink layers themselves are

not only more calcareous than the surrounding gray sediments, but also they are

observed to be more clay rich. The pink layers range from a few mm to 80 mm

thick in an east-west direction, for a distance of 23 m above a wet, gray, medium-

sand grading to gravel layer. The pink layer disappears at the corners due to

overburden, and reappears on the southwest wall for a distance of 17 m, and

generally is 3 to 4 m above limestone bedrock. One area near a folded section

presented a sequence of gray clay, pink clay, and white sand that repeated

vertically three times (Figure. 14a and b). Many sections showed a fine white discontinuous sand layer between layers of gray and brown weathered till. Peat balls were found approximately 8 cm below weathered Titusville Till; these peat

balls had a diameter of around 29 cm (Figure 14c). 34

a.)

b.)

Figure 13. Pink layers wrap around clasts. a.) Pink wrapping around large limestone clasts. b.) Pink wrapping around small clasts.

35

a.) b.) c.)

36 Figure 14. Relationship of pink diamict in the gray and brown diamict. a.) Sand layer between layers of diamict. b.) Contact between gray and weathered diamict. c.) Peat balls below a pink layer. Color was determined using a Munsell Soil Chart (1954) (Appendix A) and

yielded a gray ranging from very dark gray (5Y 3/1) to very dark grayish brown

(10YR 3/2) having the majority of samples falling into the very dark gray range.

Pink samples ranged from weak red (2.5YR 4/2) to reddish brown (2.5YR 4/4)

being mostly weak red. Brown weathered samples varied from dark yellowish

brown (10YR 4/6) to strong brown (7.5 YR 4/6) and were equally distributed

among three colors (10YR 4/6, 7.5YR 4/4, 7.5 YR 4/6), and brown units

associated with the pink layers were dark yellowish brown (10YR 4/4).

Shear planes were also observed along the high wall of the mine. They

appeared as layers of folded and deformed diamict (Figure 15a and b). These included not only gray and pink diamicts, but also some brown weathered layers.

Although overburden covered many parts of the exposure (Figure 15b), diamict

units could be traced horizontally along the high wall.

Clasts within gray and pink layers consisted of elongate rods, disks and

blades which had rounded edges. Within pink layers red shale and siltstone

clasts were fractured and smeared out. Some clasts also were aligned parallel to

the contact of the pink and gray diamict; and sizes ranged from very coarse sand

to cobbles (Figure 13a and b).

In the field gray diamicts showed a tendency to react weakly with HCl.

Their texture was siltier, sandier, and more pebbly, and generally contained

larger clasts when compared to similar parameters of pink diamicts. Pink diamicts were plastic and clay rich having some pebbles and had a moderate reaction with HCl. Brown (weathered gray) diamicts were friable, blocky, and

37

a.)

b.)

Figure 15. Deformation of tills. a.) Folding of till; section is 10 m high. b.) Layering with some deformation; section is 5 m high.

38 sandy having discontinuous sand between the layers and reacted weakly with

HCl. Pink-brown (weathered pink) diamicts were observed to be sandy and

brittle having a tendency to break along (bedding) planes and reacted weakly

with HCl.

Vertical Section Description

Samples from a vertical section taken from the bedrock to just above a

pink diamict layer were analyzed and plotted (Plate 1). The first 100 cm consisted of friable, gray, weakly calcareous, silty, sandy diamict having pebbles within 25 cm of the bedrock and obvious faceted pebbles at 50 cm. From the bedrock to 100 cm, the sediment appears to be a matrix-supported, stratified diamict (Dms). At 110 cm above the bedrock the sediment became brown and sandier before changing again at 120 cm to a gray, massive, matrix-supported diamict (Dmm) of increased clay content. At 125 cm the gray diamict has less clasts than seen previously, sand content increases slightly, and overall carbonate content drops. At 185 cm the sand content of the gray diamict declines as clay content increases, and the carbonate content begins gradually to increase. A pink layer (2.5 YR 4/2, weak red) begins at 200 cm and consists of a plastic, weakly calcareous clay diamict (Dmms) showing evidence of sheared and smeared pebbles. There is an increase in calcite and dolomite and a decrease in sand content. This layer was traced horizontally and averaged

31% sand, 43% silt and 26% clay over 14 samples. Within this layer calcite ranged from 0.0% to 3.4%, and dolomite varies between 0.3% and 6.3%.

Variations of carbonate content of the sand fraction are within the range of those

39 of all samples of pink diamict. Within this later, the mean crystalline to clastic ratio averaged 0.2, the DI averaged 1.1 having a variance of 0.05. Both ratios are within parameter ranges for all pink samples.

Textural Analysis

Textural analysis was done on 74 samples of diamict showing that there are significant differences between gray and pink diamicts. Gray diamicts contain more sand and less clay and silt than pink diamicts (Table 1). In comparing weathered diamicts, brown samples have the largest average percent of very coarse, coarse, and medium sand and the largest overall sand content of all samples. In contrast pink-brown samples have the largest mean clay content

(Table 1). Comparisons of the variances among sample groups show that the gray diamicts have the largest variance in all size fractions, very coarse (1-2 mm), coarse (0.5-1 mm), medium (0.25-0.5 mm), fine (0.125-0.25 mm), and very fine (0.063-0.125 mm) excluding clay and silt (Table 1).

Carbonate Analysis

Gasometric carbonate analysis on the silt and clay fractions and the silt fractions was done using the Chittick apparatus. Comparisons of means in both the silt and clay and silt fractions show that pink diamicts have the largest mean percent calcite, total carbonate, and calcite/dolomite ratio of all samples (Table

2). Brown diamict, weathered from gray diamict has the largest mean percent dolomite in both fractions. The silt-fraction analysis indicates that pink diamicts also have the largest means in the calcite, total carbonates and calcite/dolomite

40 Table 1. Descriptive statistics for textural analysis by color.

Fraction %vc %c %m %f % vf %Sand %Silt %Clay Gray Mean 8.2 7.6 11.5 14.9 12.1 54.9 27.6 18.2 Variance 35.6 19.3 20.5 81.6 29.1 288.5 166.8 71.9 n = 26 26 26 26 26 26 26 26

Pink Mean 4.4 4.4 6.4 7.7 8.5 31.4 42.8 25.8 Variance 6.1 2.2 4.6 9.5 9.2 114.0 51.8 113.2 n = 32 32 32 32 32 32 32 32

Brown Mean 9.7 9.8 14.8 14.2 11.9 62.9 30.0 9.7 Variance 29.9 37.5 55.8 17.7 6.3 209.1 299.1 6.7 n = 4 4 4 4 4 4 4 4

Pink-brown Mean 5.2 4.8 6.9 8.2 9.0 34.0 37.1 28.9 Variance 31.5 6.9 6.9 8.9 4.1 178.6 190.5 9.3 n = 8 8 8 8 8 8 8 8

41 Table 2. Descriptive statistics for carbonate analysis by color and size fraction.

Silt & Clay Silt % Total Total Cal % Dol Carbonate Cal/Dol % Cal % Dol Carbonate Cal/Dol Gray Mean 0.8 4.4 5.2 0.2 0.6 1.5 2.0 0.3 Variance 0.6 0.7 1.3 0.0 0.3 0.6 1.5 0.1 n = 27 27 27 27 27 27 27 27

Pink Mean 1.4 5.2 6.5 0.3 1.3 1.7 3.1 0.7 Variance 1.5 15.7 21.3 0.0 12.1 1.3 19.0 1.3

42 n = 33 33 33 33 33 33 33 33

Brown Mean 0.2 5.6 5.8 0.0 0.1 1.8 1.8 0.1 Variance 0.1 22.4 24.5 0.0 0.1 2.4 2.3 0.0 n = 6 6 6 6 6 6 6 6

Pink- brown Mean 0.8 2.6 3.5 0.2 0.6 0.8 1.4 0.6 Variance 1.0 4.5 8.9 0.0 1.0 0.1 1.4 0.9 n = 8 8 8 8 8 8 8 8

whereas the brown diamict has the largest mean in dolomite (Table 2). The

small group of brown samples exhibited more variability in dolomite in both the

silt and clay and silt fractions, whereas calcite was more variable in both fractions

of the pink samples. Variances of total carbonate and calcite/dolomite depend

on variances of calcite and dolomite.

Carbonate contents of various sand fractions were determined by the

weight-loss method. Gray diamicts have the largest mean in the very coarse-

sand fraction, and pink diamicts contain more carbonate in the other sand fractions. Brown samples contain more carbonate in the very fine-sand fractions, but both brown and pink-brown samples average less carbonate in the very- coarse, coarse, and medium-sand fractions compared to those of pink and gray diamicts (Table 3).

Variances among the various sand fractions have wide ranges. Among the four sample groups, the brown samples display less variation in the three coarsest sand fractions than the other three groups. In contrast the variance in the fine- and very fine-sand fraction of the brown diamicts are larger than the other three groups. The fine- and very-fine sand fractions are most variable in pink diamicts

(Table 3).

Clay Mineralogy

All samples taken were examined using x-ray diffraction to determine the

DI. The mean of gray diamicts is 0.9, whereas that of pink diamicts is 1.1 (Table

4). The brown weathered diamict associated with the gray diamicts have a mean

DI equal to 1.0, and the weathered pink-brown diamicts have an average DI of

43 Table 3. Descriptive statistics for carbonate analysis of sand fractions.

Sand Fraction % vc % c % m % f % vf Gray Mean 24.3 20.5 11.3 7.8 8.2 Variance 28.6 19.8 19.1 10.5 7.7 n = 26 26 26 26 26

Pink Mean 23.9 22.6 13.8 10.2 11.0 Variance 22.9 33.4 9.5 5.3 5.2 n = 32 32 32 32 32

Brown Mean 17.0 13.7 8.4 6.1 11.3 Variance 3.3 8.4 4.3 13.6 55.0 n = 5 5 5 5 5

Pink-brown Mean 17.4 16.3 10.1 8.2 10.4 Variance 53.7 52.9 17.6 10.1 11.3 n = 8 8 8 8 8

44 Table 4. Descriptive statistics for coarse-sand lithology and DI’s of glycolated samples.

Sample %Clastic %Cryst Cryst/Clast DI Glycolated Gray Mean 71.4 28.6 0.7 0.9 Variance 418.8 428.1 1.7 0.06 n = 26 26 26 27

Pink Mean 84.8 15.2 0.2 1.1 Variance 25.4 25.4 0.01 0.05 n = 32 32 32 33

Brown Mean 77.2 22.8 0.4 1.0 Variance 216.1 216.2 0.11 0.06 n = 5 5 5 6

Pink-brown Mean 85.4 14.6 0.2 2.2 Variance 13.5 13.5 0.0 0.50 n = 8 8 8 8

45 2.2. Some gray and pink samples were put through additional procedures

including x-ray diffraction analysis of air-dried, glycolated, heated to 450°C and

heated to 550°C. DIs of air-dried samples as compared to those of glycolated

samples show that little expandable clay minerals are present in gray and pink

diamicts. The heating processes facilitated in identification of crystalline chlorite, dioctehedral illite, and ordered kaolinite within samples (Starkey and others,

1984). Variances of DIs are similar for all sample groups except the pink-brown group which had a variance much larger than those of other groups (Table 4).

Coarse-Sand Lithology Analysis

Lithology of the 1-2 mm fraction was determined using a binocular microscope. Pink and pink-brown units contain more clastic rock fragments than gray and brown units. Variances of the gray and brown diamicts are much larger than those of pink and pink-brown diamicts (Table 4). After the percent clastic and percent crystalline were determined for each unit, a crystalline to clastic ratio was calculated for all of the diamicts. Gray diamicts have the largest ratio followed by the brown samples (Table 4).

Chemical Analysis

Chemical analyses of sand (Table 5) and silt and clay fractions (Table 6) of samples along with possible source rocks (Table 7) were completed and 25 of

32 elements were consistently above the detection limit. Means of each element in detectable ranges were determined for the sand and silt and clay fractions of each unit. The gray sand fraction has the largest mean in two elements (Co,

46 Cu), and the pink sand fraction also has the largest mean in two but differing elements (Ca, Mg). The brown sand fraction has the largest mean values for

nine elements (As, Fe, La, Li, Mn, Pb, Y, Zn, Zr), whereas means of the pink-

brown unit were the largest for the remaining twelve elements (Al, Ba, Be, Cr, K,

Na, Ni, P, Sc, Sr, Ti, V (Table 5)). The results were almost similar for analyses of the silt and clay fractions (Table 6) with gray silt and clay having the means of Ti and Zr as the largest. The pink silt and clay fraction has four large means, Li and

Na in addition to Ca and Mg that were also dominant in the sand fraction. The brown silt and clay fraction has nine large means consisting of those dominant elements in the sand fraction plus Ba, Co, Cu and Ni. The pink-brown diamict had ten large means (Al, Be, Cr, K, La, P, Sc, Sr, V, Y).

Variances of all elements were determined for the sand and silt and clay fractions of all units. The gray sand fraction has the largest variance in 19 of 25 cases (Table 5), whereas the brown sand fraction had the largest variances in 2 of 25 (As, Ba). In comparison the pink-brown unit had the highest variance in only 4 of 25 (Ca, Mn, Na, and Sr). The distribution of largest variances shifted when the silt and clay fractions of the unit were analyzed. The variances in the gray silt and clay fractions are largest in 9 of 25 elements (Table 6); only one element (Ti) had the largest variance in the pink diamicts. The silt and clay fraction of the brown unit has the largest variance in 11 of 25 elements (As, Ba,

CA, Co, Cu, Fe, Mg, MN, Ni, Pb, Zn); only four elements had the largest value for the pink unit (Table 6).

47 Table 5. Descriptive statistics for chemical analysis (ppm) of sand fractions.

Sample Al As Ba Be Ca Co Cr Cu Fe K La Li Gray Mean 40211.54 9.77 277.42 1.09 34076.92 55.54 30 41.07 31507.69 12853.85 20.87 27.73 Variance 130111462 11.54 4856.97 0.1 150072246 948.82 84.4 506.52 73692738 12062585 21.14 90.92 n= 26 26 26 26 26 26 26 26 26 26 26 26 Pink Mean 45971.88 8.53 328.16 1.2 35628.13 42.44 33.97 38.34 29512.5 15759.38 22.08 30.81 Variance 41882732 11.16 1720.27 0.02 82633054 548.71 29.39 130.08 20805000 5847651.2 7.61 24.22 n= 32 32 32 32 32 32 32 32 32 32 32 32 Brown Mean 45460 15 345.4 1.24 16800 33.6 33.8 39.52 37200 14000 24.88 33 Variance 27948000 43.5 5577.8 0.02 160585000 57.3 16.7 376.82 35060000 9895000 16.47 18.5 n= 5 5 5 5 5 5 5 5 5 5 5 5 Pink-brown Mean 49387.5 8.5 403.88 1.3 23250 39.63 37 40.68 31325 17212.5 24.7 31.13 Variance 22886964 12.29 2810.7 0.01 176937143 193.98 7.71 147.34 21102143 6812678.6 2.8 14.98 n= 8 8 8 8 8 8 8 8 8 8 8 8

Sample Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr

Gray Mean 10384.62 549.04 5473.08 18.81 488.46 20.73 6.06 112.53 1507.69 46.19 14.79 93.52 75.43 Variance14027754 16747 1986046.2 25.36 13061.54 41.16 4.05 783.77 103138.46 245.92 8.1 850.59 197.97 n= 26 26 26 26 26 26 26 26 26 26 26 26 26 Pink Mean 12609.38 538.5 6584.38 20.94 515.63 18.53 6.8 127.61 1625 54.5 15.47 85.42 74.7 Variance 9280877 5382.9 1054264.1 11.03 7812.5 11.61 1.08 476.13 51612.9 91.23 3.04 260 72.74 n= 32 32 32 32 32 32 32 32 32 32 32 32 32 Brown Mean 5440 757 5780 23.4 580 24.6 6.84 97.34 1700 54.8 16.88 99.52 87.5 Variance 608000 63111 1517000 13.3 2000 26.3 0.22 363.87 35000 21.7 2.45 169.73 191.93 n= 5 5 5 5 5 5 5 5 5 5 5 5 5 Pink-brown Mean 8575 559.75 7237.5 25.88 587.5 18.5 7.15 128.25 1850 61.13 16.66 80.69 83.09 Variance12887857 66535.36 2799821.4 20.7 9821.43 13.71 0.3 1035.36 60000 42.13 2.04 217.99 41.29 n= 8 8 8 8 8 8 8 8 8 8 8 8 8

48

Table 6. Descriptive statistics for chemical analyses (ppm) of silt and clay fraction.

Sample Al As Ba Be Ca Co Cr Cu Fe K La Li Gray mean 55942.86 11.86 362.25 1.51 17700 12.75 48.5 51.54 36535.71 18189.29 32.32 50.86 Variance 1.74E+08 14.94 5531.68 0.13 45005926 30.56 95.07 477.1 38147566 20532844 18.71 178.35 n= 28 28 28 28 28 28 28 28 28 28 28 28 Pink mean 62227.27 11.09 404.91 1.73 21245.45 13.15 51.94 36.05 39006.06 21118.18 33 54.33 Variance 68774545 4.52 2095.4 0.05 39847557 3.26 63.75 76.1 11456212 12962784 13.51 78.79 n= 33 33 33 33 33 33 33 33 33 33 33 33 Brown mean 52480 28.2 522.8 1.64 17160 16.8 47.4 55.58 52340 16860 36.58 48.2

49 Variance 36892000 804.7 50881.7 0.02 1.29E+08 89.2 20.3 802.34 4.59E+08 4208000 16.34 20.7 n= 5 5 5 5 5 5 5 5 5 5 5 5 Pink-brown Mean 66285.71 12 484.14 1.89 17985.71 14.86 52.57 41.29 44300 22228.57 39.76 50.57 Variance 10188095 14.67 709.48 0.01 94868095 3.81 9.95 81.63 64860000 3065714 9.48 56.29 n= 7 7 7 7 7 7 7 7 7 7 7 7

Table 6. Descriptive statistics for chemical analyses (ppm) of silt and clay fraction (continued)

Sample Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr Gray mean 9542.86 500.32 5871.43 28 603.57 20.14 9.91 100.74 2607.14 73.79 19.5 85.76 167.84 Variance 5735873 9398.08 796931.2 29.33 3320.11 8.79 5.65 223.26 119947.1 429.36 2.53 39.57 1803.33 n= 28 28 28 28 28 28 28 28 28 28 28 28 28 Pink mean 12106.06 513.18 6081.82 30.15 627.27 18.15 11.25 105.49 2527.27 87.76 19.49 80.66 137.76 Variance 6127462 2958.59 284659.1 19.32 3920.45 3.88 2.85 275.61 177670.5 244.38 1.49 29.16 258.19 n= 33 33 33 33 33 33 33 33 33 33 33 33 33 Brown mean 10640 1763.6 5180 35.6 640 40.2 10.28 89.86 2340 72.4 21.18 132.86 159.6 Variance 29333000 5335007 777000 274.3 3000 1115.2 0.73 62.23 83000 62.3 1.86 3660.55 323.3

50 n= 5 5 5 5 5 5 5 5 5 5 5 5 5 Pink- brown Mean 11014.29 760 6042.86 34.14 800 23 12.11 108.23 2414.29 95.14 21.37 109.3 129.71 Variance 10804762 263323.3 1276190 33.14 70000 59.33 0.35 323.62 104761.9 43.14 4.4 689.19 221.57 n= 7 7 7 7 7 7 7 7 7 7 7 7 7

Table 7. Results of chemical analyses (ppm) of suspected source rock.

Sample Al As Ba Be Ca Co Cr Cu Fe K La Li Grimsby shale 27700 <3 152 0.9 126000 16 18 8.3 34600 17100 43.6 25 Grimsby weathered 77100 6 414 2.5 36400 17 52 10.4 75800 35400 38.3 70 Queenston 80400 <3 441 2.2 18800 19 58 15.8 52900 37100 39 63 Grimsby 14400 <3 88 <0.5 600 145 7 6.1 2600 100 16.2 17 Black LS 2500 8 60 0.5 >15 11 8 37.1 14200 900 2.1 2 Dark gray LS 7700 6 105 0.7 >15 14 13 14.2 8600 2500 6.3 3 gray LS 2200 9 5380 <0.5 >15 6 4 8.2 10700 900 1.6 <1 Gray Queenston 66500 50 348 1.9 44200 22 42 2020 28100 31800 36.2 58

Sample Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr 51 Grimsby shale 44300 1860 600 12 2800 4 13.5 105 1400 49 59.3 54.2 92.1 Grimsby weathered 15100 700 1200 32 1500 12 14.5 86.2 2900 124 31.1 107 136 Queenston 19700 582 900 38 700 12 14.7 92 3000 126 21.3 82.4 104 Grimsby <0.01 17 <0.01 1 300 4 2 224 300 3 5.8 4.9 51 Black LS 4100 1030 200 9 1100 11 <0.5 481 100 9 2.6 246 4.1 Dark gray LS 5600 788 300 25 800 17 1.4 757 200 14 6.1 27.1 9.7 gray LS 4700 479 200 5 100 <2 <0.5 689 3 1.6 7.1 3.7 Gray Queenston 20000 817 1400 42 800 10 12.7 79.5 2400 118 30.3 72.1 145

CHAPTER V

DISCUSSION

Field observations (mainly color, texture and reaction to HCl) were used to

determine groupings of samples; gray, pink, brown and pink-brown. Statistical

analysis was used to compare pink to gray diamicts and also their relationship to

brown and pink-brown samples. Additionally, gray and pink diamicts were

compared to possible source rocks. F and t tests were done on laboratory-

measured parameters to determine the probability of significant differences (P <

0.05) between combinations of diamicts.

F tests were done to determine the equality of variances of textures within pairings of different colors (Table 8). The gray diamict had significantly different variances in all textural measures when compared to pink diamicts (Table 8).

Gray diamicts had larger variances than pink diamicts in all categories except clay (Table 9). Additionally, gray diamicts were more variable when compared to the brown and pink-brown groups. Brown and pink-brown were divided equally on the number of rejected F tests with brown having the larger variances for 6 of

8 parameters in the comparisons of brown to pink-brown and to pink samples. In comparing pink-brown to pink samples, F tests were rejected in 5 of 8 cases

(Table 8), and pink samples showed more variation than pink-brown (Table 9).

52 Table 8. F tests comparing variances in size fractions between different groups (+ signifies significant difference at P < 0.05). g = gray, p = pink, b = brown, pb = pink-brown

Sand Fraction % < 2 mm Comparison % vc % c % m % f % vf % sand % silt % clay g/p + + + + + + + + b/pb + + + + g/b + + + + g/pb + + + + b/p + + + + + pb/p + + + + +

53 Table 9. Groups having the larger variances in size fractions when comparing various combinations of groups (+ signifies the high variance by color).

Sand Fraction % < 2 mm Larger Comparison variance % vc % c % m % f % vf % sand % silt % clay g/p gray + + + + + + + b/pb brown + + + + + + g/b gray + + + + + g/pb gray + + + + + + b/p brown + + + + + + pb/p pink + + + 54 T tests were performed to test the equality of means of textural

parameters for various combinations of sample groups (Table 10). Means of

gray and pink diamicts are significantly different in all categories; gray diamicts

have the larger means in all sand fractions and in total sand content (Table 11).

The gray and brown samples differ only in the clay content, whereas means of all

parameters are similar for pink and pink-brown samples (Table 10). Means of clay percentages are significantly different for all combinations. Gray and brown samples generally have larger mean percentages in their sand fractions when compared to pink and to pink-brown samples (Table 11). These comparisons may allow us to assume that the brown and pink-brown were weathered versions of the gray and pink respectively.

Further study of the texture using a trilinear graph (Figure 16) displays the overall textural distribution of pink and gray diamict samples and their means.

This display additionally shows that the pink diamicts concentrate in the silt and clay portion, and the gray diamicts tend to cluster toward the sand portion of the graph.

F tests on the carbonate data were performed on sand, silt, and silt and clay fractions of all groups to detect significant differences in variances between the groups of diamicts. In comparing pink and gray diamicts variances are significantly different for coarse, medium, and fine sand (Table 12). In the 4 of 6 comparisons, variances of calcite differed in the < 0.074 mm fractions (Table 13), but only calcite differed for the pink and pink-brown comparisons in the silt fraction (Table 14). Variances of the dolomite in the silt fraction rejected in three

55 Table 10. Results of t tests comparing means of all size fractions between different combinations of groups (+ signify significant difference at P < 0.05).

Sand Fraction % < 2mm % vc % c % m % f % vf % sand % silt % clay Comparison g/p + + + + + + + + b/pb + + + g/b + g/pb + + + + + b/p + + + pb/p

56 Table 11. Groups having the larger means when comparing textural parameters using various combinations of groups (+ signifies the high variance by color).

Sand Fraction % < 2 mm Larger Comparison mean % vc % c m % % f % vf % sand % silt % clay g/p gray + + + + + + b/pb brown + + + + + + g/b gray + + + g/pb gray + + + + + + b/p brown + + + + + + pb/p pink +

57

58

Figure 16. Trilinear plot of textural data. (+ = gray diamict, = pink diamict, red symbol = mean). Table 12. F tests comparing variances in carbonate contents of the sand fractions between different groups (+ signifies significant difference at P < 0.05).

Sand Fraction Comparison % vc % c % m % f % vf g/p + + + b/pb + + g/b + + g/pb + + b/p + + + pb/p +

59 Table 13. F tests comparing variances in carbonate contents of the silt and clay fractions (% < 0.74 mm)(+ signifies significant difference).

Silt and Clay Fractions Comparison % Cal % Dol Total Carb g/p + b/pb + g/b + g/pb + b/p + + pb/p +

60 Table 14. F tests comparing variances in carbonate content of the silt fraction (+ signify significant difference at P < 0.05).

Silt Fraction Comparison % Cal % Dol Total Carb Cal/Dol g/p b/pb + g/b + + g/pb + b/p + + pb/p +

61 comparisons (Table 14). Gray units had the larger variances in carbonate

contents of sand fractions when compared to pink and brown units (Table 15).

Gray and brown units had larger variances in the < 0.074 mm fraction in only 6 of

24 possible cases (Table 16). Within the silt fraction, dolomite had the larger variance in 4 of 5 combinations involving gray and brown samples (Table 17).

T tests were performed to test the equality of means of carbonates in all size fractions. The carbonate means were similar for the very coarse and coarse sand fractions for the gray and pink diamict and for the brown to pink-brown comparisons (Table 18). Means are statistically equal for all sand fractions for the brown to pink-brown comparisons. Means are similar for the three finest sand fractions in comparing gray to brown diamicts and gray to pink-brown diamicts. Equality of means was rejected for calcite and dolomite in the < 0.074 mm fraction for the gray to pink comparison and results vary for other combinations (Table 19). Differences between means in calcite and dolomite may affect results of t tests for total carbonate and calcite/dolomite. For the silt fraction only 4 of 12 comparisons of calcite and dolomite demonstrate significantly different means (Table 20). Calcite differs for the pink to gray comparison, but dolomite differs in the last three combinations.

In examining comparisons of diamicts, gray means were larger in 7 of 10 cases in comparing gray means to those of brown or pink-brown samples (Table

21). Pink diamicts have larger means compared to those of the gray or pink- brown diamicts when considering the < 0.074 mm fractions and the silt fractions

62 Table 15. Groups having the larger variances in carbonate content when comparing various combinations of groups in various sand fractions (+ signify the high variance by color).

Sand Fraction Larger Comparison variance % vc % c % m % f % vf g/p gray + + + + b/pb brown + + g/b gray + + + g/pb gray + b/p brown + + pb/p pink

63 Table 16. Groups having the larger variances in carbonate content of the <0.074 mm fraction when comparing various combinations of groups (+ signifies the large variance by color).

Silt & Clay (% < 0.074) Larger Total Comparison variance % cal % dol Carb Cal/Dol g/g gray b/pb brown + + g/b gray + + g/pb gray b/g brown + + pb/g pink +

64 Table 17. Groups having the larger variances in carbonate content in silt fractions when comparing various combinations of groups (+ signify the high variance by color).

Silt Fraction Larger Comparison variance % Cal % Dol Total Carb Cal/Dol g/p gray + b/pb brown + + g/b gray + + g/pb gray + + b/p brown + pb/p pink + + +

65 Table 18. T tests comparing means in carbonate content of the sand fractions (+ signifies significant difference at P < 0.05).

Sand Fraction

Comparison % vc % c % m % f % vf g/p + + + b/pb g/b + + g/pb + + b/p + + + + pb/p + + + +

66 Table 19. T tests comparing means in carbonate contents of the < 0.074 mm fractions (+ signifies significant difference at P < 0.05).

% < 0.074 mm fraction % % Total Comparison Cal Dol Carb Cal/Dol g/p + + + b/pb g/b + + g/pb + + b/p + + pb/p + +

67 Table 20. T tests comparing means in carbonate content of the silt fractions (+ signifies significant difference at P < 0.05).

Silt fraction Comparison % Cal % Dol Total Carb Cal/Dol g/p + + + b/pb g/b + g/pb + b/p + + pb/p + +

68 Table 21. Groups having the larger means when comparing carbonate contents of sand fractions of various combinations of groups (+ signifies the high variance by color).

Sand Fraction Larger Comparison mean % vc % c % m % f % vf g/p gray + b/pb brown + g/b gray + + + + g/pb gray + + + b/p brown + pb/p pink + + + + +

69 alone (Table 22, 23). There are slight differences between Tables 22 and 23 for other comparisons.

Comparisons of clay mineralogy were made using glycolated slides of the clay fractions. F tests showed that the variances were equal in most combinations with the exception of gray to brown comparison, which shows a significant difference in variance (Table 24). When comparing the combinations, the larger variances differ when pink diamicts were compared to gray and brown diamicts (Table 25). The t tests showed that means of most of the combinations were similar except for the means of gray diamicts compared to pink and pink- brown diamicts, and the pink diamicts compared to pink-brown diamicts (Table

26). Generally the DIs of samples having a pink coloration are larger than those of gray or brown samples. Additionally, mean DIs of brown samples and pink- brown samples are larger than gray and pink samples because chlorite has weathered producing a relative increase in illite (Table 27).

After the coarse-sand lithology was determined by counting approximately

300 grains in each sample, a crystalline to clastic ratio was determined but its validity is uncertain. The crystalline to clastic ratio was equal within the pink and pink-brown samples but the gray is almost twice that of the brown. Means were determined for each and that of the gray and brown diamicts were comparable as were those of the pink and pink-brown. F tests were performed on crystallines and clastics in very coarse-sand fractions to determine the equality of the variances (Table 24). All of the F tests rejected except gray compared to brown,

70 Table 22. Groups having the larger means when comparing carbonate contents of the < 0.074 of various combinations of groups (+ signify the high variance by color).

% < 0.074 mm fraction Larger % % Total Cal/Dol Comparison mean Cal Dol Carb g/p pink + + + + b/pb brown + + g/b gray + + g/pb gray + + + + b/p brown + pb/p pink + + + +

71 Table 23. Groups having the larger means when comparing the silt fractions of various combinations (+ signifies the high variance by color).

Silt fraction Larger % Total Comparison mean Cal % Dol Carb Cal/Dol g/g pink + + + + b/pb brown + + g/b gray + + + g/pb gray + + b/g brown + pb/g pink-gray + + + +

72 Table 24. F tests comparing variances in coarse-sand lithologies and DIs between groups (+ signifies significant difference).

Comparisons Clastic Crystalline Crystalline/Clastic DI g/g + + + b/pb + + + g/b + + g/pb + + + b/g + + + pb/p

73 Table 25. Groups having the larger variances when comparing various combinations of groups within the coarse-sand lithologies and DIs (+ signifies the high variance by color).

Larger Comparisons variance Clastic Crystalline Crystalline/Clastic DI g/p gray + + + + b/pb brown + + + g/b gray + + + g/pb gray + + + b/g brown + + + + pb/p pink + + +

74 Table 26. T tests comparing means in coarse-sand lithologies and DIs (+ signifies significant difference).

Comparisons Clastic Crystalline Crystalline/Clastic DI g/p + + + b/pb g/b g/pb + + + b/pp + pb/p +

75 Table 27. Group having the larger means in the coarse-sand lithologies and DI when comparing various combinations of groups (+ signifies the high mean by color).

Larger Comparisons mean Clastic Crystalline Crystalline/Clastic DI g/p gray + + b/pb brown + + g/b gray + + g/pb gray + + b/p brown + + pb/p pink + +

76 T tests were completed to determine equality of the means on the clastic and crystalline grains in the very coarse-sand fractions (Table 26); gray to pink and gray to pink-brown comparisons rejected on both tests. The brown to pink comparison rejected in the crystalline category and once again the larger means were either gray or brown depending on the comparisons (Table 27).

A 32-element chemical analysis of both the sand and silt and clay fractions shows that composition of pink diamicts differs significantly from that of gray diamicts. F tests performed on the sand fractions rejected for 19 of 25 elements when comparing gray and pink diamicts (Table 28) and gray diamicts have the larger variances in all 25 elements in this comparison (Table 29).

Within silt and clay fractions, 17 of 25 F tests were rejected in the pink to gray comparison (Table 30); gray diamicts had the larger variances (Table 31) for 21 elements in the pink to gray comparison.

T tests performed on elements in the sand fraction rejected for 7 of 25 elements (Table 32) in the pink to gray comparisons with gray having the larger means for 8 elements (Table 33). Fourteen of 25 means differed for the gray to pink brown comparison (Table 32), but 17 of 25 means were larger for the brown diamict compared to pink diamict (Table 33). T tests for the silt and clay fractions resulted with 12 of 25 tests rejecting for the gray to pink and gray to pink-brown comparisons (Table 34). Gray diamicts have the larger means in 7 of 25 comparisons to pink diamicts, but 13 elements have larger means when the brown diamicts are compared to the pink diamicts (Table 35).

77 Table 28. F tests comparing variances in chemical analyses of sand fractions (+ signifies significant difference).

Comparisons Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p + + + + + + + + + + + + + + + + + + + b/pb + + + + + + + + + + g/b + + + + + + + + g/pb + + + + + + + + + + + + + + + + + b/p + + + + + + + + + + + + + + + pb/p + + + + + + + + + + + + + +

78 Table 29. Group having the larger variances when comparing chemical analyses of various combinations of groups within the sand fractions (+ signifies the high variance by color).

Larger Comparisons variance Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p gray + + + + + + + + + + + + + + + + + + + + + + + + + b/pb brown + + + + + + + + + + + + + g/b gray + + + + + + + + + + + + + + + + + + + + g/pb gray + + + + + + + + + + + + + + + + + + + + b/p brown + + + + + + + + + + + + pb/p pink + + + + + + + + + + 79 Table 30. F tests comparing variances in chemical analyses of silt and clay fractions (+ signifies significant difference).

Comparisons Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p + + + + + + + + + + + + + + + + + b/pb + + + + + + + + + + + + + + g/b + + + + + + + + g/pb + + + + + + + + + + + + + + + + + + b/p + + + + + + + + + + + + + + + + + + + + + + pb/p + + + + + + + + + + + 80 Table 31. Groups having the larger variances when comparing chemical analyses of various combinations of groups within the silt and clay fractions (+ signifies the high variance by color).

Comparisons Larger variance Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p gray + + + + + + + + + + + + + + + + + + + + + b/pb brown + + + + + + + + + + + + + + + + + + + g/b gray + + + + + + + + + + + + + + + g/pb gray + + + + + + + + + + + + + + + b/p brown + + + + + + + + + + + + + + + 81

Table 32. T tests comparing means of chemical analyses of sand fractions (+ signifies significant difference).

Comparisons Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p + + + + + + + b/pb + + + g/b + + + + + + g/pb + + + + + + + + + + + + + + b/p + + + + + + + p/pb + + + + + + + + + 82 Table 33. Groups having the larger means when comparing chemical analyses of various combinations of groups within sand fractions (+ signifies the high variance by color).

Comparisons Larger mean Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p gray + + + + + + + + b/pb brown + + + + + + + + + g/b gray + + + + + + g/pb gray + + + + + + + + b/p brown + + + + + + + + + + + + + + + + + p/pb pink + + + + + +

83 Table 34. T tests comparing means in chemical analyses of silt and clay fractions (+ signifies significant difference).

Comparisons Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p + + + + + + + + + + + + b/pb + + + + + + + + g/b + + + + + + + + g/pb + + + + + + + + + + + + b/p + + + + + + + pb/g + + + + + + + + + + 84 Table 35. Groups having the larger means for chemical analyses when comparing various combinations of groups within the silt and clay fractions (+ signifies the high variance by color).

Larger Comparisons mean Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr g/p gray + + + + + + + b/pb brown + + + + + + + + + + g/b gray + + + + + + + + g/pb gray + + + + + b/p brown + + + + + + + + + + + + + p/pb pink + + + + + +

85 Elemental analyses were compared between size fractions within each color group. F tests were rejected for 20 of 25 elements in the gray group (Table

36) and 14 of 25 elements in the pink group. The brown group had more elements with similar variances. Within the pink and gray groups, the same 12 elements have larger variances in the same fractions and include bulk elements and trace elements (Table 37). In a similar fashion, t tests rejected for 18 of the same elements in the pink and gray diamicts (Table 38). Means within the brown group rejected only 9 elements. Table 39 shows that the silt and clay fractions have larger means for more elements than the sand fraction, which may suggest comminution of the sand fraction within the size fractions

Correlation coefficients of element pairings were determined to help identify source rocks. For both the sand and silt and clay fractions, each element was correlated to every other element. There are 300 possible pairings for which correlation coefficients were calculated. Statistically to determine significance at

P <0.05, the choice was made to eliminate all negative correlations and those below the significant correlation coefficient of 0.39 in the gray sand fraction and those below 0.35 in the pink sand fraction. For the gray silt and clay fraction,

0.37 was the smallest significant r, and 0.34 was the smallest value for pink silt and clay. For comparisons of the elements in gray sand fraction (Table 40), 208 pairs of elements were determined to be significant, whereas within the pink sand fraction, 153 pairs of elements were determined significant (Table 40). The number of significant correlation coefficients was less

86 Table 36. F tests comparing variances in chemical analyses between size fractions within each color group (+ signifies significant difference).

Comparisons Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr gray + + + + + + + + + + + + + + + + + + + + pink + + + + + + + + + + + + + + brown + + + + + + + + + + + pink-brown + + + + + + + + + + + + +

87

Table 37. Size fractions having the larger variances when comparing chemical analyses of size fractions within the same color (+ signifies the high variance by color).

Comparisons Larger variance Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr gray sand + + + + + + + + + + + + + pink sand + + + + + + + + + + + + + brown sand + + + + + + pink-brown sand + + + + + + + + + 88 Table 38. T tests comparing means for chemical analyses of size fractions within the same color (+ signifies significant difference).

Comparisons Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr gray + + + + + + + + + + + + + + + + + + pink + + + + + + + + + + + + + + + + + + + + brown + + + + + + + + + pink-brown + + + + + + + + + + + + + + + +

89

Table 39. Groups having the larger means for chemical analyses when comparing size fractions within the same color (+ signifies the high mean by color).

Larger Comparisons mean Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr gray silt & clay + + + + + + + + + + + + + + + + + + pink silt & clay + + + + + + + + + + + + + + + + + brown silt & clay + + + + + + + + + + + + + + + + + + + + + + pink-brown silt & clay + + + + + + + + + + + + + + + + + + + + + 90 Table 40. Correlation matrix for elemental comparisons in the sand fractions.

Gray Sand n = 26 significant r = 0.39

ANALYTE Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr - - Al 0.39 0.94 0.94 0.44 0.51 0.97 0.11 0.67 0.96 0.86 0.90 0.67 0.54 0.31 0.93 0.52 0.39 0.97 0.71 0.94 0.99 0.82 0.40 0.75 - - As 0.14 0.56 0.30 0.30 0.46 0.06 0.85 0.25 0.64 0.67 0.17 0.64 0.36 0.64 0.63 0.67 0.53 0.14 0.27 0.48 0.66 0.36 0.71 - - Ba 0.81 0.37 0.44 0.90 0.15 0.40 0.96 0.69 0.72 0.68 0.32 0.48 0.79 0.31 0.13 0.86 0.74 0.92 0.90 0.65 0.22 0.54 - - Be 0.32 0.47 0.95 0.08 0.81 0.83 0.92 0.93 0.49 0.58 0.02 0.94 0.55 0.51 0.98 0.54 0.86 0.97 0.84 0.51 0.80 - - Ca 0.39 0.36 0.10 0.45 0.58 0.43 0.53 0.90 0.75 0.65 0.51 0.79 0.20 0.35 0.86 0.29 0.42 0.70 0.13 0.50 ------Co 0.40 0.10 0.49 0.50 0.55 0.51 0.46 0.47 0.18 0.51 0.51 0.16 0.48 0.44 0.43 0.49 0.57 0.21 0.59 - Cr 0.08 0.67 0.91 0.84 0.88 0.59 0.46 0.17 0.95 0.48 0.36 0.97 0.62 0.89 0.98 0.77 0.42 0.72 ------Cu 0.01 0.15 0.04 0.05 0.23 0.00 0.15 0.03 0.04 0.14 0.08 0.14 0.12 0.10 0.01 0.13 0.04

91 - Fe 0.52 0.86 0.87 0.38 0.84 0.20 0.82 0.79 0.72 0.77 0.39 0.54 0.73 0.88 0.57 0.87

K 0.75 0.82 0.82 0.50 0.54 0.86 0.51 0.23 0.88 0.85 0.89 0.92 0.78 0.27 0.64

La 0.93 0.50 0.70 0.02 0.91 0.71 0.63 0.88 0.53 0.76 0.87 0.90 0.60 0.94

Li 0.60 0.71 0.10 0.95 0.71 0.62 0.91 0.60 0.75 0.91 0.91 0.54 0.89

Mg 0.60 0.76 0.64 0.63 0.07 0.55 0.95 0.55 0.62 0.69 0.07 0.47

Mn 0.19 0.64 0.91 0.59 0.56 0.64 0.45 0.57 0.88 0.39 0.76 - - Na 0.12 0.19 0.26 0.10 0.78 0.34 0.20 0.24 0.25 0.03

Ni 0.68 0.49 0.95 0.63 0.80 0.95 0.89 0.52 0.84

P 0.56 0.54 0.64 0.38 0.55 0.88 0.48 0.82

Pb 0.44 0.09 0.32 0.41 0.57 0.45 0.68

Sc 0.59 0.90 0.99 0.83 0.47 0.77

Sr 0.65 0.67 0.73 0.08 0.50

Ti 0.92 0.72 0.32 0.65

V 0.84 0.43 0.76

Y 0.50 0.93

Zn 0.59

Zr

Table 40 (continued). Correlation matrix for elemental comparisons in the sand fractions.

Pink Sand n = 32 significant r = 0.35

ANALYTE Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr - - Al 0.14 0.87 0.86 0.28 0.39 0.93 0.37 0.50 0.95 0.73 0.80 0.51 0.75 0.55 0.74 0.61 0.18 0.98 0.49 0.91 0.97 0.88 0.17 0.66 ------As 0.31 0.13 0.38 0.22 0.07 0.15 0.49 0.23 0.29 0.09 0.40 0.29 0.47 0.36 0.01 0.06 0.06 0.47 0.22 0.09 0.01 0.36 0.28 - - Ba 0.61 0.38 0.19 0.77 0.36 0.31 0.93 0.47 0.50 0.64 0.74 0.80 0.57 0.63 0.15 0.79 0.72 0.87 0.83 0.83 0.08 0.40 - - Be 0.01 0.45 0.89 0.24 0.68 0.71 0.88 0.91 0.19 0.69 0.13 0.75 0.58 0.30 0.93 0.09 0.70 0.88 0.85 0.49 0.84 ------Ca 0.16 0.12 0.13 0.55 0.47 0.12 0.10 0.93 0.01 0.62 0.15 0.25 0.05 0.19 0.84 0.22 0.18 0.06 0.38 0.31 ------Co 0.37 0.29 0.31 0.34 0.53 0.51 0.27 0.27 0.05 0.30 0.33 0.08 0.42 0.01 0.15 0.35 0.38 0.36 0.42

Cr 0.24 0.55 0.85 0.72 0.84 0.33 0.68 0.37 0.78 0.55 0.24 0.96 0.29 0.84 0.97 0.84 0.26 0.72

Cu 0.16 0.32 0.28 0.23 0.18 0.23 0.28 0.30 0.18 0.28 0.37 0.25 0.33 0.30 0.34 0.09 0.16 - - - Fe 0.31 0.75 0.55 0.32 0.56 0.16 0.73 0.71 0.26 0.57 0.33 0.44 0.55 0.75 0.56 0.86 -

92 K 0.55 0.63 0.68 0.69 0.76 0.63 0.55 0.09 0.88 0.71 0.90 0.92 0.78 0.02 0.45 - - La 0.86 0.09 0.65 0.02 0.68 0.66 0.34 0.80 0.06 0.51 0.73 0.84 0.62 0.88

Li 0.23 0.54 0.01 0.67 0.41 0.36 0.88 0.04 0.60 0.81 0.74 0.49 0.82 - - - Mg 0.30 0.76 0.03 0.07 0.01 0.40 0.92 0.44 0.41 0.23 0.30 0.10

Mn 0.44 0.43 0.83 0.17 0.73 0.29 0.73 0.75 0.88 0.17 0.65 - - - Na 0.16 0.33 0.11 0.39 0.93 0.66 0.49 0.37 0.45 0.11

Ni 0.53 0.19 0.77 0.06 0.66 0.78 0.73 0.30 0.70

P 0.12 0.58 0.12 0.57 0.62 0.85 0.30 0.65 - Pb 0.24 0.07 0.11 0.20 0.25 0.43 0.37

Sc 0.34 0.85 0.97 0.89 0.28 0.75 - - Sr 0.53 0.40 0.22 0.47 0.22 - Ti 0.91 0.82 0.02 0.58

V 0.89 0.19 0.71

Y 0.33 0.83

Zn 0.60

Zr for silt and clay fraction (Table 41). Within the gray silt and clay, 105 pairs were determined significant, and within the pink silt and clay fraction 173 pairs of elements were determined significant (Table 41).

Means of elements were determined for each class of diamict (Table 5 and 6) and compared to the values from the suspected source rocks (Table 7) to examine origin of the diamicts. Percent differences were calculated when

comparing mean values of elements in sand and silt and clay fractions of each color to measured values of these elements for suspected source rocks (Table

42). Generally differences were large, but there were a few similarities. Within the gray sand fraction Fe, Sr, Ti and V were within + 10% of the rock value for

the Grimsby Shale, and Ca was within 10% of that value for weathered Grimsby

Shale. The Queenston Shale and gray sand were within 10% of each other for

Mn concentrations. The arsenic content of the gray sand fraction is within 10%

of the value of As in the gray Vanport Limestone. Values of Sr, Fe, and K for the

gray silt and clay fraction are within 5% of measured values for those elements in the Grimsby Shale. The Cr value for gray silt and clay fraction is within 10% of the Cr content of the weathered Grimsby Shale.

The pink silt and clay fraction elemental concentractions tended to be closer to the rock values when compared. They were within 5% of values for the

Grimsby Shale in Sr and within 5% for Ba, Cr, and Zr values for the weathered

Grimsby Shale. The pink diamict was also within 10% of Ni values of the weathered Grimsby Shale. The pink samples were within 5% of the values for the gray Queenston Shale in Al, Be, La, and Li and within 10% of Ti and Zr and

93

Table 41. Correlation matrix for elemental comparisons in the silt and clay fractions.

Gray Silt and Clay n = 28 significant r = 0.37

ANALYTE Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr ------Al 0.31 0.98 0.99 0.13 0.04 0.93 -0.14 0.20 0.95 0.75 0.92 0.50 0.18 0.51 0.84 0.21 0.08 1.00 0.56 0.75 0.97 0.17 0.10 0.54 ------As 0.26 0.24 0.56 0.43 0.34 -0.07 0.75 0.26 0.51 0.24 0.15 0.66 0.23 0.03 0.43 0.33 0.28 0.19 0.56 0.24 0.21 0.30 0.22 ------Ba 0.99 0.08 0.04 0.93 -0.16 0.27 0.94 0.74 0.91 0.53 0.11 0.45 0.84 0.10 0.07 0.99 0.60 0.75 0.96 0.11 0.12 0.54 ------Be 0.07 0.03 0.92 -0.22 0.28 0.94 0.69 0.92 0.52 0.12 0.50 0.85 0.16 0.10 0.99 0.60 0.71 0.97 0.22 0.11 0.60 ------Ca 0.71 0.18 -0.27 0.65 0.06 0.51 0.13 0.52 0.77 0.36 0.05 0.49 0.19 0.10 0.67 0.42 0.04 0.35 0.05 0.58 ------Co 0.22 -0.33 0.47 0.00 0.43 0.03 0.25 0.46 0.27 0.00 0.06 0.09 0.03 0.39 0.52 0.02 0.80 0.35 0.75 ------Cr -0.09 0.14 0.95 0.70 0.91 0.58 0.17 0.25 0.91 0.02 0.12 0.93 0.47 0.81 0.94 0.03 0.02 0.38 ------Cu -0.14 0.17 0.20 0.10 0.26 0.11 0.15 0.05 0.03 0.54 0.14 0.36 0.06 0.12 0.40 0.23 0.40 - - - - 94 Fe 0.26 0.15 0.25 0.23 0.74 0.08 0.40 0.54 0.20 0.23 0.64 0.19 0.26 0.21 0.42 0.58 ------K 0.62 0.92 0.23 0.06 0.26 0.91 0.03 0.20 0.96 0.65 0.70 0.98 0.14 0.01 0.57 - - - La 0.59 0.11 0.41 0.44 0.50 0.29 0.07 0.74 0.21 0.86 0.67 0.32 0.15 0.03 ------Li 0.53 0.13 0.41 0.89 0.06 0.03 0.92 0.43 0.61 0.92 0.19 0.14 0.53 - - - - Mg 0.22 0.21 0.62 0.27 0.47 0.53 0.69 0.31 0.60 0.18 0.20 0.55 - - - - - Mn 0.37 0.04 0.71 0.19 0.16 0.50 0.34 0.12 0.07 0.33 0.34 ------Na 0.16 0.69 0.17 0.48 0.00 0.23 0.37 0.52 0.39 0.39 - - - Ni 0.11 0.05 0.86 0.53 0.57 0.90 0.11 0.13 0.51 - - - P 0.15 0.18 0.29 0.15 0.13 0.38 0.08 0.03 - - - - Pb 0.10 0.25 0.18 0.11 0.05 0.55 0.11 - - Sc 0.58 0.75 0.98 0.16 0.10 0.55 - - Sr 0.32 0.58 0.16 0.04 0.70 - Ti 0.71 0.37 0.15 0.03 - - V 0.16 0.07 0.56 - Y 0.20 0.79 - Zn 0.23

Zr

Table 41(continued). Correlation matrix for elemental comparisons in the silt and clay fractions.

Pink Silt and Clay n = 33 significant r = 0.34

ANALYTE Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Na Ni P Pb Sc Sr Ti V Y Zn Zr - - Al 0.19 0.98 0.97 0.57 0.93 0.91 0.22 0.89 0.98 0.61 0.91 0.78 0.75 0.16 0.97 0.19 0.15 0.99 0.76 0.75 0.98 0.63 0.37 0.51 ------As 0.22 0.17 0.48 0.10 0.19 -0.05 0.05 0.26 0.17 0.03 0.47 0.67 0.42 0.12 0.32 0.21 0.17 0.49 0.22 0.17 0.28 0.25 0.21 - Ba 0.95 0.57 0.90 0.89 0.33 0.89 0.96 0.57 0.84 0.80 0.78 0.25 0.93 0.30 0.19 0.96 0.79 0.71 0.96 0.66 0.39 0.54 - Be 0.47 0.94 0.95 0.18 0.86 0.95 0.60 0.93 0.70 0.70 0.03 0.97 0.11 0.17 0.98 0.67 0.76 0.97 0.60 0.42 0.44 - - - Ca 0.53 0.47 -0.12 0.35 0.65 0.20 0.38 0.95 0.75 0.60 0.48 0.19 0.36 0.51 0.92 0.43 0.55 0.28 0.34 0.65 - Co 0.90 0.05 0.86 0.93 0.69 0.90 0.72 0.64 0.04 0.94 0.18 0.10 0.95 0.69 0.79 0.92 0.63 0.37 0.38 - Cr 0.15 0.79 0.91 0.54 0.87 0.69 0.70 0.07 0.94 0.13 0.20 0.93 0.67 0.83 0.90 0.62 0.38 0.34 - Cu 0.30 0.19 0.03 0.03 0.05 0.30 0.27 0.17 0.38 0.53 0.18 0.13 0.03 0.24 0.31 0.55 0.10 - Fe 0.86 0.54 0.75 0.59 0.55 0.20 0.86 0.39 0.20 0.87 0.61 0.64 0.86 0.73 0.57 0.40 - 95 K 0.56 0.86 0.84 0.78 0.26 0.95 0.25 0.06 0.97 0.83 0.77 0.97 0.63 0.28 0.54 - La 0.76 0.32 0.25 0.29 0.67 0.03 0.30 0.63 0.34 0.70 0.60 0.48 0.45 0.07 - - - Li 0.58 0.54 0.22 0.94 0.10 0.20 0.93 0.53 0.75 0.90 0.47 0.38 0.31 - - - Mg 0.86 0.56 0.70 0.27 0.19 0.74 0.98 0.58 0.77 0.46 0.11 0.68 - Mn 0.50 0.66 0.37 0.04 0.71 0.86 0.58 0.73 0.57 0.11 0.49 - - - Na 0.01 0.56 0.18 0.07 0.64 0.05 0.15 0.32 0.19 0.43 - Ni 0.12 0.17 0.98 0.67 0.80 0.96 0.61 0.40 0.41 - P 0.12 0.17 0.40 0.23 0.13 0.66 0.30 0.06 - Pb 0.15 0.14 0.13 0.14 0.24 0.58 0.28 - Sc 0.71 0.77 0.98 0.63 0.39 0.45 - - Sr 0.63 0.74 0.56 0.05 0.61

Ti 0.73 0.76 0.34 0.02 - V 0.59 0.36 0.50

Y 0.52 0.09

Zn 0.20

Zr

Table 42. Comparisons of elemental compositions of source rocks to those of size fraction of diamicts of various colors. Numbers are percent differences. (BD = below detection)

Rock Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Gray sand Grimsby Shale 145.17 B D 182.52 120.94 27.05 212980.77 166.67 494.86 91.06 75.17 47.87 110.92 23.44 29.52 Grimsby Shale(weathered) 52.16 162.82 67.01 43.54 93.62 200452.49 57.69 394.93 41.57 36.31 54.49 39.62 68.77 78.43 Grimsby Formation 279.25 B D 315.25 B D 5679.49 23501.33 428.57 673.33 1211.83 12853.85 128.82 163.12 B D 3229.64 Gray Queenston 60.47 19.54 79.72 57.29 77.10 154895.10 71.43 2.03 112.13 40.42 57.65 47.81 51.92 67.20 Red Queenston 50.01 B D 62.91 49.48 181.26 179352.23 51.72 259.96 59.56 34.65 53.51 44.02 52.71 94.34 Black LS 1608.46 122.12 462.37 217.69 B D 309790.21 375.00 110.71 221.89 1428.21 993.77 1386.54 253.28 53.30 Dark Gray LS 522.23 162.82 264.21 155.49 B D 243406.59 230.77 289.25 366.37 514.15 331.26 924.36 185.44 69.67 Gray LS 1827.80 108.55 5.16 B D B D 567948.72 750.00 500.89 294.46 1428.21 1304.33 B D 220.95 114.62

Pink sand Grimsby Shale 165.96 B D 215.89 133.68 28.28 222675.78 188.72 461.90 85.30 92.16 50.65 123.25 28.46 28.95 Grimsby Shale(weathered) 59.63 142.19 79.26 48.13 97.88 209577.21 65.32 368.63 38.93 44.52 57.65 44.02 83.51 76.93 Grimsby Formation 319.25 B D 372.90 B D 5938.02 24571.12 485.27 628.48 1135.10 15759.38 136.30 181.25 B D 3167.65 Gray Queenston 69.13 17.06 94.30 63.32 80.61 161946.02 80.88 1.90 105.03 49.56 61.00 53.13 63.05 65.91 Red Queenston 57.18 B D 74.41 54.69 189.51 187516.45 58.57 242.64 55.79 42.48 56.62 48.91 64.01 92.53 96 Black LS 1838.88 106.64 546.93 240.63 B D 323892.05 424.61 103.34 207.83 1751.04 1051.49 1540.63 307.55 52.28 Dark Gray LS 597.04 142.19 312.53 171.88 B D 254486.61 261.30 269.98 343.17 630.38 350.50 1027.08 225.17 68.34 Gray LS 2089.63 94.79 6.10 B D B D 593802.08 849.22 467.53 275.82 1751.04 1380.08 B D 268.28 112.42

Rock Na Ni P Pb Sc Sr Ti V Y Zn Zr Gray sand Grimsby Shale 912.18 156.73 17.45 518.27 44.87 107.17 107.69 94.27 24.94 172.54 81.90 Grimsby Shale(weathered) 456.09 58.77 32.56 172.76 41.78 130.54 51.99 37.25 47.55 87.40 55.46 Grimsby Formation B D 1880.77 162.82 518.27 302.88 50.24 502.56 1539.74 254.97 1908.56 147.90 Gray Queenston 390.93 44.78 61.06 207.31 47.70 141.54 62.82 39.15 48.81 129.71 52.02 Red Queenston 608.12 49.49 69.78 172.76 41.21 122.31 50.26 36.66 69.43 113.49 72.53 Black LS 2736.54 208.97 44.41 188.46 B D 23.39 1507.69 513.25 568.79 38.02 1839.68 Dark Gray LS 1824.36 75.23 61.06 121.95 432.69 14.86 753.85 329.95 242.43 345.09 777.60 Gray LS 2736.54 376.15 488.46 B D B D 16.33 B D 1539.74 924.28 1317.17 2038.57

Pink sand Grimsby Shale 1097.40 174.48 18.42 463.28 50.35 121.53 116.07 111.22 26.09 157.59 81.11 Grimsby Shale(weathered) 548.70 65.43 34.38 154.43 46.88 148.04 56.03 43.95 49.74 79.83 54.93 Grimsby Formation B D 2093.75 171.88 463.28 339.84 56.97 541.67 1816.67 266.70 1743.18 146.47 Gray Queenston 470.31 49.85 64.45 185.31 53.52 160.51 67.71 46.19 51.05 118.47 51.52 Red Queenston 731.60 55.10 73.66 154.43 46.24 138.71 54.17 43.25 72.62 103.66 71.83 Black LS 3292.19 232.64 46.88 168.47 B D 26.53 1625.00 605.56 594.95 34.72 1821.95 Dark Gray LS 2194.79 83.75 64.45 109.01 485.49 16.86 812.50 389.29 253.59 315.19 770.10 Gray LS 3292.19 418.75 515.63 B D B D 18.52 B D 1816.67 966.80 1203.04 2018.92

Table 42. Comparisons of elemental compositions of source rocks to those of size fraction of diamicts of various colors. Numbers are percent differences. (BD = below detection) (continued).

Rock Al As Ba Be Ca Co Cr Cu Fe K La Li Mg Mn Gray silt and clay Grimsby Shale 201.96 B D 238.32 168.25 14.05 79.69 269.44 620.91 105.59 106.37 74.13 203.43 21.54 26.90 Grimsby Shale(weathered) 72.56 197.62 87.50 60.57 48.63 75.00 93.27 495.54 48.20 51.38 84.39 72.65 63.20 71.47 Grimsby Formation 388.49 B D 411.65 B D 2950.00 8.79 692.86 844.85 1405.22 18189.29 199.51 299.16 B D 2943.07 Gray Queenston 84.12 23.71 104.09 79.70 40.05 57.95 115.48 2.55 130.02 57.20 89.29 87.68 47.71 61.24 Red Queenston 69.58 B D 82.14 68.83 94.15 67.11 83.62 326.18 69.07 49.03 82.88 80.73 48.44 85.97 Black LS 2237.71 148.21 603.75 302.86 B D 115.91 606.25 138.91 257.29 2021.03 1539.12 2542.86 232.75 48.57 Dark Gray LS 726.53 197.62 345.00 216.33 B D 91.07 373.08 362.93 424.83 727.57 513.04 1695.24 170.41 63.49 Gray LS 2542.86 131.75 6.73 B D B D 212.50 1212.50 628.48 341.46 2021.03 2020.09 B D 203.04 104.45

Pink silt and clay Grimsby Shale 224.65 B D 266.39 192.26 16.86 82.20 288.55 434.32 112.73 123.50 75.68 217.33 27.33 27.59 Grimsby Shale(weathered) 80.71 184.85 97.80 69.21 58.37 77.36 99.88 346.62 51.46 59.66 86.15 77.62 80.17 73.31 Grimsby Formation 432.13 B D 460.12 B D 3540.91 9.07 741.99 590.96 1500.23 21118.18 203.68 319.61 B D 3018.72 Gray Queenston 93.57 22.18 116.35 91.07 48.07 59.78 123.67 1.78 138.81 66.41 91.15 93.68 60.53 62.81 Red Queenston 77.40 B D 91.82 78.65 113.01 69.22 89.55 228.15 73.74 56.92 84.61 86.24 61.45 88.18 97 Black LS 2489.09 138.64 674.85 346.06 B D 119.56 649.24 97.17 274.69 2346.46 1571.28 2716.67 295.27 49.82 Dark Gray LS 808.15 184.85 385.63 247.19 B D 93.94 399.53 253.86 453.56 844.73 523.76 1811.11 216.18 65.12 Gray LS 2828.51 123.23 7.53 B D B D 219.19 1298.48 439.62 364.54 2346.46 2062.31 B D 257.58 107.14

Rock Na Ni P Pb Sc Sr Ti V Y Zn Zr Gray silt and clay Grimsby Shale 978.57 233.33 21.56 503.57 73.44 95.95 186.22 150.58 32.88 158.22 182.24 Grimsby Shale(weathered) 489.29 87.50 40.24 167.86 68.37 116.87 89.90 59.50 62.70 80.15 123.41 Grimsby Formation B D 2800.00 201.19 503.57 495.71 44.97 869.05 2459.52 336.21 1750.15 329.10 Gray Queenston 419.39 66.67 75.45 201.43 78.07 126.72 108.63 62.53 64.36 118.94 115.75 Red Queenston 652.38 73.68 86.22 167.86 67.44 109.50 86.90 58.56 91.55 104.07 161.38 Black LS 2935.71 311.11 54.87 183.12 B D 20.94 2607.14 819.84 750.00 34.86 4093.64 Dark Gray LS 1957.14 112.00 75.45 118.49 708.16 13.31 1303.57 527.04 319.67 316.45 1730.30 Gray LS 2935.71 560.00 603.57 B D B D 14.62 B D 2459.52 1218.75 1207.85 4536.20

Pink silt and clay Grimsby Shale 1013.64 251.26 22.40 453.79 83.37 100.47 180.52 179.10 32.87 148.82 149.57 Grimsby Shale(weathered) 506.82 94.22 41.82 151.26 77.62 122.38 87.15 70.77 62.67 75.38 101.29 Grimsby Formation B D 3015.15 209.09 453.79 562.73 47.10 842.42 2925.25 336.05 1646.13 270.11 Gray Queenston 434.42 71.79 78.41 181.52 88.62 132.70 105.30 74.37 64.33 111.87 95.01 Red Queenston 675.76 79.35 89.61 151.26 76.56 114.67 84.24 69.65 91.51 97.89 132.46 Black LS 3040.91 335.02 57.02 165.01 B D 21.93 2527.27 975.08 749.65 32.79 3359.94 Dark Gray LS 2027.27 120.61 78.41 106.77 803.90 13.94 1263.64 626.84 319.52 297.64 1420.18 Gray LS 3040.91 603.03 627.27 B D B D 15.31 B D 2925.25 1218.18 1136.06 3723.18

within 5% of values of the red Queenston Shale for Zn and within 10% for Ba and

Y. Local source rocks showed values that were within 5% for Cu in the black

limestone clast found within a pink layer and within 5% for Cr for the local dark gray limestone. The values were also within 10% of the value for the black limestone clast for Pb and within 10% of Mn value of the local gray limestone.

The pink sand fraction did not contain as many close comparisons but did show some values that were within the 10% tolerance. Potassium is within 10% of the content of the Grimsby Shale and within 5% for Ca in the weathered

Grimsby Shale. The gray Queenston Shale is within 10% for Ba and Fe, and the

red Queenston Shale value is within 5% of Zn the value and 10% of value of the

pink sand fraction Mn. The local black limestone also has values that are within

5% of the Cu and Y values and within 10% of the As mean. The dark gray

limestone was within 10% of Pb value of the pink sand fraction. This fraction was

also within 10% of the As value of the gray limestone.

These values may suggest that the pink diamicts have a source in the

Grimsby and Queenston formations with some contribution of local source rocks

to the elemental composition of the pink diamicts (Table 41). Pink fragments of

shale and siltstone were noted in the sand fractions of the pink diamicts and

support these hypotheses. The gray diamicts tend to have a similar chemistry to

the Grimsby and Queenston formations, but also show possible larger

contributions from the local source rocks within their sand and silt and clay

fractions.

98 Source Area

Statistical analysis of most measured laboratory parameters implies that

the pink and gray diamicts have different source areas. The differences between

the pink and gray diamicts were consistently different allowing their identification

using textural, carbonate, x-ray diffraction and chemical analysis. Textural data

from this study were compared to those of Szabo and Totten (1995). Their means for Titusville Till averaged 34% sand, 46% silt and 20% clay, whereas combined pink and gray samples from the study area had means off 43% sand,

35% silt and 22% clay. However the matrix texture of gray diamicts averaged

55% sand, 28% silt and 18% clay, which appear to be larger than the regional

values in the sand fraction. This may be due to incorporations of local sandstone of the Plateau. The average matrix texture of pink diamicts differs from regional

averages and contains 31% sand, 43% silt, and 26% clay.

The pink diamicts are more clay rich than the gray diamicts. There are

two possibilities for the finer texture of pink diamicts. First, part of the texture of

pink diamicts may be inherited from source rocks. Their color and observations

of the pink color of various sand fractions during laboratory analysis suggests

that pink diamict is derived from shales and siltstones. Secondly some crushing

of these pink rocks may have not only occurred during transport but also during

deposition. Although Dreimanis and Vagners (1971) determined that diamicts

having more terminal grades in mineral modes reflect a more mature till, some

mineral modes may be inherited from original rocks. In contrast the gray diamicts have larger percentages within sand fractions when compared to pink diamicts.

99 This may imply that more local bedrock was incorporated into the gray diamict along the flow path. Local bedrock would be preserved in the sand fraction representing a shorter transport distance (Dreimanis and Vagners, 1971).

Matrix texture was also used to determine the parent material of weathered diamicts. Means of the gray and brown diamicts show that these two groups are statistically equivalent. Likewise, comparisons of the pink and pink- brown groups also are statistically similar in all fractions except clay. The brown and pink-brown samples are considered a weathered product of the gray and pink diamicts. However the number of samples is small. There are five brown samples and eight pink-brown samples that may not be representative of their respective populations. These weathered diamicts occur in layers and may have been altered by oxygenated ground water.

Results of analyses of carbonate contents of the pink and gray diamicts were distinctly different. Generally gray diamicts contained more carbonate in the very coarse-sand fractions than the pink diamicts. Gray diamicts have more variance in carbonate contents than pink diamicts. This variance may be caused by the incorporation of local limestone into gray diamicts, increasing the calcite content in the coarser fractions and causing more variability within this group.

Pink diamicts have larger variances in all fractions except coarse sand when compared to those of the gray diamicts. This implies that pink diamicts have a different source of carbonates than gray diamicts. Dreimanis and Vagners,

(1971), suggest that the silt fraction is the terminal grade for carbonate.

However, in this study, there is a significant carbonate content within the clay

100 fraction. Because glaciers do not have enough available energy to reduce

carbonates to clay-size particles (Drewery, 1986), clay-size carbonates must be

inherited from the source rocks. This again suggests a different source area for

the pink diamict.

DIs also differed between the pink and gray diamicts. The mean of the

gray diamict is 0.9, whereas that of the pink diamict is 1.1; these are significantly

different, but both samples groups show a range in DIs (Table 4). The brown

weathered diamict associated with the gray diamicts had a mean DI equal to 1.0, whereas the weathered pink-brown diamicts have an average DI of 2.2.

Variances of DIs are similar for all sample groups except the pink-brown group which had a much larger variance than that of the other group. The regional average DI for the Titusville Till is 0.9 (Szabo and Totten, 1995). Values less than 1.0 represent the incorporation of local Pennsylvanian-age rock containing more kaolinite than the older illitic Paleozoic rocks (Szabo and Fernandez, 1984;

Volpi and Szabo, 1988). Bruno (1988) found that the DIs of Upper Ordovician red and gray Queenston Shale and Lower Silurian Grimsby Formation range from 2.1 to 2.6. Pink diamicts contain more illite than gray diamicts, some values fall within the range published by Bruno (1988). DI values for the pink diamicts are somewhat lower possibly because of minor incorporation of other source rocks.

Analysis of the 1-2 mm fractions shows differences between diamicts; pink and pink-brown units contain more clastic rock fragments than the gray and brown units. However, many of the clastic fragments are pink siltstones and

101 shales that may have been formed locally through crushing. Sheared and fragmented pink clasts were observed in pink layers in the field. Pink diamicts contain less crystalline rock fragments than gray diamicts. Gray diamicts have a significantly larger crystalline to clastic ratio than pink diamicts. The crystalline fragments may represent a long distance transport component, which may have been augmented by locally reworked crystalline erratics from earlier glaciations.

Analyses of the elemental composition of the diamicts produced complicated results. Elemental composition differed in two ways. Means of most elements in the sand fraction of the gray and pink diamicts were significantly different suggesting a different source area for both diamicts. A similar conclusion may be drawn for the silt and clay fraction of the diamicts. These differences may not only result from differing source areas but also from the interaction of rock properties and glacial processes. These elements may be contained in rock fragments and also in mineral fragments. Reduction of minerals to terminal grade depends upon original size, hardness, cleavage, and presence of weak zones along mineral boundaries in rock fragments (Dreimanis and Vagners, 1971).

The elemental composition of diamicts in the study area has three possible sources. First, Matz (1996) determined that the Grenville Province of the Canadian Shield was a source of heavy minerals in the Titusville Till. Matz also found that the amphibole group was dominated by green hornblende and the garnet population was of the purple variety originating in the eastern Grenville

Province.

102 A second extra local source is the Niagara Peninsula. Elemental analysis

of Queenston and Grimsby formations of that area suggest a relationship to the

pink diamict. Mean values of the elemental analyses within the pink silt and clay

fractions show that values within the Grimsby Shale being within a 10% tolerance of the Grimsby Shale for Ba, Cr, Ni, Sr, and Zr. The Queenston shale values

also were within tolerance for Al, Be, La, Li, Ti, Zn, and Zr with Ba. The sand

fraction had less tolerable values, but was within tolerance for Ca and K contents

of the Grimsby Formation, and within Ba, Fe, and Mn content of the Queenston

Formation.

The third source is local rocks that contributed primarily to the composition

of the gray diamicts. Large amounts of carbonate in coarse sand fractions

suggest local rocks, and DI values less than 1.0 imply incorporation of local

shales. The larger variances of measurement values in the gray diamicts

suggests mixing of rocks of all three source areas asd melt out occurred.

Mechanism of placement

The thinly bedded nature of the pink diamict and its areal distribution is

suggestive of a mode of origin different than lodgment or meltout processes.

Thin layers of pink are indicative of shear planes. Shearing in high walls is

implied by the presence of sheared, smeared, and fractured fine-grained clasts

within the pink layers. Many layers of folded pink diamict could be traced

laterally along the wall. The pink diamict appeared to have been plastic or ductile

wrapping around clasts in many layers. Pink layers appear to be separated by

103 layers of matrix-supported, stratified diamict. This sequence repeats itself

upward suggesting deposition of pink layers in a meltout sequence.

The vertical section (Plate 1) shows textural and compositional differences

between pink and gray diamicts. Within the vertical section bulges occur in two

locations: one at 125-cm level and then another at the 205-cm level (pink layer).

The 125-cm level represents a switch from Dmm to Dms experienced as a change in the texture, carbonate content and element concentrations at this point

(Plate 1). The 205-cm bulge is at the pink layer and contrasts significantly with

the gray diamict. There may be some mixing near the contact of the pink and

gray diamicts, because measured elemental parameters began to increase

towards the pink margins.

After deposition of a lodgment till on the limestone bedrock, subglacial

melt out released a stratified diamict that was overlain by a sheared layer of pink

diamict. Moran (1967, 1971) recognized sheared layers in a pit north of the

study area as repetitive sequences of similar textures and quartz-feldspar ratios.

It is likely that if the high wall could have been sampled vertically, a similar

sequence of repetitive measures may have been observed in the sequence. It

was observed that a sequence similar to that of the measuredvertical section

repeated at least three times.

Figure 17 illustrates a possible mode of emplacement of the pink layers.

The initial cut in the study area was dominated by pink diamicts and resembled

the larger orange units thrust stacked on the right of the diagram. The pink layer in successive cuts in the study area may represent the up ice source of the

104 Ice Flow 105

Figure 17. Diagram representing thrust stacking (modified from: http://www.geus.dk/publications/bull/nr8/nr8_p148-192- dk.htm).

orange layers along shear planes on the left of the diagram. Future work in order to verify these findings and to examine the possible repetitive nature of the pink diamict in vertical sections should be conducted.

106 CHAPTER VI

CONCLUSION

The pink and gray diamicts have different source areas. Because the gray diamict is coarser textured, and the pink diamict more clay rich, the source area of the gray diamict is much closer to the depositional site than that of the pink diamict. Carbonate content is residing generally in the silt fraction of both diamicts, but some clay-size carbonate in the pink diamict is inherited from transported pink shale. DIs are numerically close, but statistically show significant differences; the pink diamicts have larger values that approach those of the Grimsby and Queenston formations, whereas the gray diamicts are representative of the local bedrock. Crystalline to clastic ratios show that the gray diamict contains more crystalline rock fragments than the pink diamicts, suggesting that the source bed of the pink diamicts remained intact in the ice.

The elemental analysis supports the similarities of the Grimsby and Queenston formations to the pink diamicts. The sources of the pink diamicts are considered to be a combination of Grimsby and Queenston formations, whereas the gray diamicts incorporated the local Pennsylvanian bedrock, that mixed with far- traveled crystalline rocks as the ice melted.

Ice originating in Grenville Province flowed across Niagara Peninsula and incorporated slabs of the Queenston and Grimsby formations. These blocks 107 were lifted into the englacial zone and transported into eastern Ohio within the

Grand River Lobe. As ice melted, englacial slabs of the pink formations were lowered into active zone at base of glacier and sheared upward in the terminus.

The combination of shearing and meltout led to the alteration of gray and pink diamicts seen in the exposure

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112

APPENDICES

113

APPENDIX A FIELD DESCRIPTIONS OF SAMPLES

Sample # ID Color # Color Name Pic # HCl rxn Description General partly Bedrock site info 10/03/2006 cloudy, PIC 1-3 N42E, 62 diamict clast supported NE face above above bedrock, pebbles increase in layers, silty sand, poorly 1 bedrock 5y 3/1 Very dark gray weak sorted, 2 cm thick pebbles silty sand, poorly sorted, possible melt out, pebbles

114 layered below 25 cm., faceted stones at 50 cm, friable up to 50 2 +25cm 10YR 5/2 grayish brown weak cm. 3 +50cm 10YR 3/2 very dark grayish brown weak rocky, brown 4 +75cm 10YR 3/2 very dark grayish brown weak not as many clasts 5 +100cm 10YR 4/2 dark grayish brown weak silty sand with some clasts 6 110cm(1.1) 10YR 4/6 dark yellowish brown weak sandy 7 120cm(1.2) 10YR 4/1 dark gray weak massive diamict looks like large ball in wall 8 125cm(1.25) 10YR 4/2 dark grayish brown 3-6 weak silty sand less clast 9 150cm(1.5) 10YR 5/2 grayish brown weak loosing clast, sandy 10 175cm(1.75) 10YR 5/2 grayish brown weak loose sandy 11 185cm(1.85) 10YR 4/2 dark grayish brown weak coarse grain, below clay layer 12 190cm(1.9) 10YR 4/1 dark gray weak silty clay 13 195cm(1.95) 10YR 4/1 dark gray weak clayey silt 14 200cm(2P) 2.5YR 4/2 weak red moderate pink clay, plastic 15 205cm(2.05P) 10YR 3/1 very dark gray weak large grain size 16 205cm(2.05R) 2.5y 4/0 dark gray weak start site info 210cm(2.10) orange 17 220cm(2.20) 7.5YR 4/4 brown/dark brown weak 18 250cm(2.5) 7.5YR 4/6 strong brown large grain size 19 25wp 2.5YR 4/2 brown/dark brown moderate stones parallel to contact, pink clay 20 50wp 2.5YR 4/2 brown/dark brown moderate pink clay, some pebbles 21 75wp 2.5YR 4/2 brown/dark brown 11 moderate pink clay, some pebbles 22 100wp 2.5YR 4/2 brown/dark brown moderate pink clay, some pebbles 23 125wp 2.5YR 4/2 brown/dark brown moderate pink clay, some pebbles site info after 125cm 12 &13 pink seems to end APPENDIX A FIELD DESCRIPTIONS OF SAMPLES (CONTINUED)

Sample # ID Color # Color Name Pic # HCl rxn Description 24 250wp 2.5YR 4/2 brown/dark brown moderate pink starts again, had stone on top (flat horizontal) 25 275wp 2.5YR 4/2 brown/dark brown 14-18 moderate pink clay,some pebbles, black limestone in layer 26 25ep 2.5YR 4/2 brown/dark brown moderate pebbly 27 50ep 2.5YR 4/2 brown/dark brown moderate pebbles within 28 75ep 2.5YR 4/2 brown/dark brown 19 & 20 moderate gray thickens, pink around 4 cm 29 100ep 2.5YR 4/2 brown/dark brown moderate gray thickens, pink around 4cm red enters brown, becomes brittle, brown w/red doesn't effervesce 30 125ep 10YR 4/4 dark yellowish brown weak as well, no longer red in gray red enters brown, becomes brittle, brown w/red doesn't effervesce 31 150ep 10YR 4/4 dark yellowish brown weak as well, no longer red in gray red enters brown, becomes brittle, brown w/red doesn't effervesce 32 175ep 10YR 4/4 dark yellowish brown weak as well, no longer red in gray, broke on bedding plane 33 200ep 10YR 4/4 dark yellowish brown red/brown sits on top of gray 34 225ep 10YR 4/4 dark yellowish brown enters gray with carbonate clasts again 115 35 250ep 10YR 4/4 dark yellowish brown red starts to split 36 275ep 10YR 4/4 dark yellowish brown 21 & 22 red is split, sample from upper boundary, wavy and diffuse 37 300ep 10YR 4/4 dark yellowish brown red taken from lower split, about 2 to 3 cm site info 23 to 29 taken of site 38 325epu thickens to about 6cm 39 350epl 40 12 ft east 3'1" above limestone 40 E12'0 silty sand w/clasts 41 E12' +20cm finer silty sand w/clasts 42 E12' +25cm moderate red plastic same as other red 43 E12' +35cm 2.5YR 4/0 dark gray moderate red gray more diffuse, same as above site info last two samples appear to be red with gray in the middle site info 30 &31 boulder surrounded by clay w/pockets of sand (silly sand) 44 E12' +55 clay to east of boulder, sand stringer under sample weak to 45 E12' +65 2.5YR 4/0 dark gray moderate clay gray 46 E12' +75 strike N40W pebble axis, dip NW33, dip up ice 47 E12' +85 right below contact, gray sandy 48 E12' +100 brown sandy E about 5- site info 6m(22.5') 32 -34 red returns to brown clay red is line between brown and gray gray 5y 50 1/0 3/1 very dark gray 1-6 gray-slight top of the lower contact with red, pink 49 2.5YR 4/4 reddish brown pink-moderate about 2cm, plastic, blocky, few pebbles gray 5y gray-sandier, slight reaction, moderate pebbles, loose, some 51 1+5cm 3/1 very dark gray slight clay,clayey sand, grades into sand above APPENDIX A FIELD DESCRIPTIONS OF SAMPLES (CONTINUED)

Sample # ID Color # Color Name Pic # HCl rxn Description iron- stained color change, base hard centered orange to red site info 1+10cm. 10YR 5/6 yellowish brown slight (hematite cement), grades into sandy layer gray 5y 52 1 - 20cm 3/1 very dark gray same as sample 1 pink 53 2.5YR 4/4 reddish brown 54 1-25cm turns to sand 3.048 m over,10cm above 0, grab sample had brown sand, about 55 GS1 7-8 4ft above stone site info GS2 brown clay w/red 56 GS2+5cm stratified above gray (brown) 57 gray 58 GS2+10cm Orange/red/wh 116 59 ite white sand with red with gray sand 60 red &gray clay 0.61 m above white sand 61 gray clay white sand red at base 62 red large above white sand blocky, very horizontal slabs break apart about 4cm. w/sand layer btwn evidence of shearing, discontinuous sand layers within 63 End Samples samples top 25' gray w/red and brown w/red, cycle-gray clay-red-sand-clay- 64 Samples from other end red-sand 65 red contact 66 interface 67 gray w/red 68 side pit gray clay 69 11/28 above notch 70 11/28 below notch 71 bag of samples

APPENDIX B DATA FROM TEXTURAL ANALYSES OF ALL SAMPLES

SAMPLE Color % vc %c %m %f %vf % Sand % Silt % Clay 1 gray 3.2 3.5 15.1 36.4 19.6 77.7 12.3 9.9 2 gray 8.6 9.9 16.5 20.4 15.2 70.6 14.7 14.7 3 gray 9.5 8.3 15.8 19.1 12.7 65.4 10.1 24.5 4 gray 4.6 5.3 22.2 28.3 13.0 73.5 7.7 18.9 5 gray 3.0 4.1 13.8 28.0 24.5 73.4 15.9 10.8 7 gray 8.3 9.1 12.0 11.1 9.1 49.6 28.1 22.3 8 gray 6.7 8.1 11.7 20.3 23.3 70.2 21.6 8.2 9 gray 4.6 5.2 17.9 30.9 18.9 77.5 19.0 3.5 10 gray 9.5 7.4 14.3 28.3 18.6 78.0 16.1 5.9 11 gray 24.0 19.7 17.7 12.5 7.6 81.5 8.1 10.4 12 gray 10.6 7.8 11.6 14.2 13.3 57.6 35.4 7.0 13 gray 6.8 5.8 8.7 10.5 10.5 41.8 31.8 26.4 15 gray 24.5 19.2 12.0 5.8 4.6 66.1 13.3 20.7 16 gray 15.9 11.9 8.1 5.7 5.2 46.8 25.2 28.1 45 gray 3.3 3.8 6.5 8.5 9.8 31.9 47.8 20.3 46 gray 4.2 3.9 5.0 5.9 7.1 26.1 45.7 28.2 47 gray 8.2 10.3 14.0 11.5 9.9 53.9 29.1 17.0 50 gray 2.5 3.6 5.3 6.0 7.9 47.7 40.1 34.6 51 gray 6.1 6.2 10.9 13.4 13.9 50.5 35.9 13.6 52 gray 5.2 4.7 6.4 8.0 8.7 43.7 46.4 20.5 54 gray 9.0 8.5 14.2 18.6 15.1 41.2 21.9 12.6 57 gray 5.4 5.4 7.1 7.2 7.6 41.7 43.7 23.5 63 gray 3.2 3.5 5.0 5.7 6.8 24.2 40.6 35.1 68 gray 3.9 4.3 7.6 10.4 12.4 38.6 38.6 22.8 69 gray 16.7 12.9 11.1 7.2 6.7 54.6 30.7 14.7 70 gray 4.4 4.9 9.1 12.2 12.7 43.3 38.1 18.6 Average 8.2 7.6 11.5 14.9 12.1 54.9 27.6 18.2 Variance 42.0 25.3 32.1 93.5 40.5 340.7 195.4 90.7 n= 26 26 26 26 26 26 26 26 6 brown 8.7 10.4 22.7 19.2 10.8 71.7 20.7 7.5 17 brown 16.7 18.0 19.4 14.3 9.2 77.7 12.1 10.2 56 brown 3.4 3.7 7.0 8.9 12.4 46.0 51.4 13.2 66 brown 9.9 7.0 10.0 14.3 15.1 56.3 35.7 8.0 Average 9.7 9.8 14.8 14.2 11.9 62.9 30.0 9.7 Variance 38.6 44.5 65.8 32.0 17.1 265.4 319.8 14.7 n= 4 4444 4 4 4 14 pink 3.7 3.9 4.8 5.1 5.7 23.2 37.1 39.7 19 pink 3.4 3.9 4.7 5.0 5.8 22.8 31.7 45.6 20 pink 3.4 3.8 5.2 5.4 6.2 24.0 33.6 42.4 21 pink 3.7 4.3 5.8 6.1 6.9 26.9 47.3 25.8 22 pink 4.9 4.6 6.9 7.4 7.9 31.6 50.5 17.8 23 pink 4.1 4.4 6.6 7.9 8.3 31.4 26.8 41.8 24 pink 4.8 4.7 7.2 8.5 8.8 33.9 50.1 16.0

117 APPENDIX B DATA FROM TEXTURAL ANALYSES OF ALL SAMPLES (CONTINUED)

SAMPLE Color % vc %c %m %f %vf % Sand % Silt % Clay 25 pink 4.2 4.6 6.4 7.5 7.8 30.4 53.5 16.1 26 pink 3.3 3.7 5.4 6.1 7.1 25.6 51.3 23.1 27 pink 3.4 3.8 4.9 5.3 6.4 23.9 51.1 25.0 28 pink 3.8 4.4 5.6 6.4 6.8 26.9 41.1 31.4 29 pink 4.9 4.4 6.3 6.8 6.8 29.2 41.8 29.0 34 pink 3.9 4.4 6.5 7.0 7.9 29.8 39.9 30.3 35 pink 3.2 4.1 5.5 6.3 7.3 26.5 41.7 31.9 36 pink 3.1 3.9 5.0 5.7 6.9 24.5 42.8 32.7 37 pink 3.4 3.9 5.4 5.9 7.0 25.7 42.6 31.7 38 pink 3.7 4.1 5.4 6.1 7.4 26.5 42.1 31.4 39 pink 3.0 4.0 5.2 5.7 6.9 25.0 44.4 30.6 40 pink 16.0 11.3 15.7 16.2 12.1 71.3 23.0 5.7 41 pink 4.8 3.6 7.5 16.8 20.5 53.3 42.0 4.6 42 pink 3.3 3.7 5.4 6.3 7.4 26.1 49.1 24.8 43 pink 3.5 4.0 5.3 5.9 7.5 26.3 52.9 20.8 44 pink 3.7 3.5 6.2 9.5 13.3 36.2 50.2 13.6 49 pink 3.2 3.0 4.1 4.8 6.2 21.3 41.8 36.9 53 pink 5.0 4.4 6.1 7.6 8.0 31.0 44.0 25.0 59 pink 8.4 5.3 8.7 14.5 12.8 49.9 39.5 10.7 60 pink 2.4 2.8 3.9 4.6 6.3 19.9 45.8 34.3 61 pink 6.7 5.4 8.1 10.6 11.5 42.3 47.9 9.8 62 pink 7.4 7.1 9.8 9.1 9.4 42.8 37.2 19.9 65 pink 3.4 3.9 7.2 8.6 9.4 32.5 45.4 22.1 67 pink 3.5 3.9 6.9 9.7 12.5 36.5 44.4 19.1 71 pink 3.0 3.8 5.5 6.4 8.1 26.7 37.8 35.5 Average 4.4 4.4 6.3 7.6 8.4 31.3 42.9 25.8 Variance 9.8 6.2 10.3 15.9 16.6 140.9 94.5 138.6 n= 32 32 32 32 32 32 32 32 30 pink-brown 3.6 4.1 5.4 6.4 7.5 27.0 44.0 29.0 31 pink-brown 3.9 4.5 5.4 5.7 7.2 26.7 43.9 29.4 32 pink-brown 3.0 3.5 5.5 7.2 9.9 29.1 46.2 24.7 33 pink-brown 4.6 5.0 7.0 6.4 6.8 29.8 37.2 33.0 48 pink-brown 18.9 11.1 13.0 14.2 8.6 65.8 4.2 30.1 55 pink-brown 2.8 3.7 7.1 9.9 11.2 34.8 35.7 29.5 58 pink-brown 2.4 3.1 4.8 5.8 8.2 24.3 44.5 31.1 64 pink-brown 2.1 3.3 6.8 10.2 12.5 34.7 41.3 24.0 Average 5.2 5.0 6.9 7.9 8.5 33.9 36.5 29.5 Variance 35.1 11.0 12.4 15.3 12.3 207.7 234.4 38.8 n= 88888 8 8 8

118

APPENDIX C DATA FOR CARBONATE ANALYSES OF SAND, SILT, AND SILT AND CLAY FRACTIONS

Sand Silt and Clay Silt SAMPLE Color % vc % c % m % f % vf % silt % clay % Cal % Dol Total Carb Cal/Dol % Cal % Dol Total Carb Cal/Dol 1.0 gray 30.9 20.5 8.3 6.9 8.4 0.3 4.9 0.6 4.7 5.2 0.1 0.0 0.3 0.3 0.0 2.0 gray 22.0 17.4 7.8 5.6 7.8 1.9 2.9 0.2 4.5 4.8 0.1 0.5 1.4 1.9 0.4 3.0 gray 25.9 22.3 9.8 6.5 7.7 1.3 3.9 0.6 4.7 5.2 0.1 0.5 0.8 1.3 0.6 4.0 gray 28.7 20.2 7.1 5.9 7.6 2.7 1.6 0.4 3.9 4.3 0.1 0.4 2.3 2.7 0.2 5.0 gray 21.7 17.8 6.8 4.7 6.1 2.3 2.7 0.6 4.4 5.0 0.1 0.4 1.9 2.3 0.2 119 7.0 gray 25.2 19.4 10.3 6.4 6.8 1.1 4.7 0.0 5.8 5.8 0.0 0.3 0.9 1.1 0.3 8.0 gray 19.0 20.2 9.6 5.0 5.7 1.9 1.9 0.0 3.9 3.8 0.0 0.4 1.5 1.9 0.2 9.0 gray 21.0 17.2 6.5 5.0 6.7 5.6 0.0 0.2 4.3 4.5 0.1 2.1 3.5 5.6 0.6 10.0 gray 22.3 18.6 7.7 4.8 6.2 4.1 0.4 0.0 4.5 4.5 0.0 1.2 2.9 4.1 0.4 11.0 gray 23.1 21.5 11.1 7.1 7.5 2.8 1.4 0.0 4.2 4.2 0.0 0.6 2.2 2.8 0.3 12.0 gray 21.5 20.7 8.6 5.9 6.9 1.5 3.2 0.2 4.5 4.7 0.1 0.9 0.6 1.5 1.5 13.0 gray 22.2 18.4 9.4 6.6 7.4 1.4 3.6 0.6 4.4 5.0 0.1 0.3 1.1 1.4 0.3 15.0 gray 24.0 15.0 23.5 9.5 10.0 1.6 4.1 1.1 4.6 5.7 0.2 0.0 1.6 1.5 0.0 16.0 gray 28.1 25.8 14.9 10.2 10.6 2.5 3.7 1.3 4.9 6.2 0.3 0.5 2.0 2.5 0.3 45.0 gray 24.1 22.9 11.8 8.5 9.4 3.2 4.6 2.3 5.5 7.8 0.4 1.3 1.9 3.2 0.7 46.0 gray 23.7 22.1 15.6 11.7 13.0 1.9 4.7 1.8 4.8 6.6 0.4 0.5 1.4 1.9 0.4 47.0 gray 8.9 8.1 5.2 4.3 7.6 0.6 3.4 0.4 3.6 4.0 0.1 0.0 0.6 0.6 0.0 50.0 gray 36.7 30.1 19.6 15.7 15.0 2.7 5.4 3.0 5.0 8.1 0.6 1.2 1.5 2.7 0.8 51.0 gray 32.1 22.7 10.9 6.8 6.1 1.4 3.4 0.9 3.8 4.8 0.3 0.0 1.4 1.3 0.0 52.0 gray 25.5 19.7 10.4 7.5 8.9 1.5 3.0 0.6 3.9 4.5 0.2 0.1 1.3 1.5 0.1 54.0 gray 22.0 20.6 9.5 5.7 6.6 2.4 2.6 0.6 4.4 5.0 0.1 0.0 2.4 2.3 0.0 57.0 gray 27.9 21.4 12.9 8.4 10.3 2.4 3.1 1.5 4.0 5.5 0.4 0.2 2.2 2.4 0.1 63.0 gray 30.0 30.1 17.5 12.7 13.0 3.6 1.5 1.9 3.2 5.1 0.6 1.6 0.4 0.1 0.0 68.0 gray 27.2 25.4 13.9 8.0 9.7 3.7 2.9 1.3 5.3 6.6 0.2 1.4 2.3 3.7 0.6 69.0 gray 19.0 19.6 15.6 16.6 1.1 0.7 2.6 1.0 2.3 3.3 0.5 0.0 0.7 0.7 0.0 70.0 gray 19.4 16.4 8.4 5.8 7.1 0.3 4.0 1.5 2.7 4.3 0.6 0.0 0.3 0.3 0.0 74.0 gray 2.2 3.5 0.0 5.7 5.7 0.0 0.9 1.2 2.2 0.8 Mean 24.3 20.5 11.3 7.8 8.2 2.1 3.1 0.8 4.4 5.2 0.2 0.6 1.5 2.0 0.3 Variance 28.6 19.8 19.1 10.5 7.7 1.5 1.8 0.6 0.7 1.3 0.0 0.3 0.6 1.5 0.1 n= 26 26 26 26 26 27 27 27 27 27 27 27 27 27 27 6.0 brown 16.7 10.6 5.1 4.4 5.9 2.4 0.6 0.0 3.0 3.0 0.0 0.7 1.7 2.4 0.4 17.0 brown 17.2 14.3 9.6 8.2 13.0 2.0 11.9 0.5 13.4 13.9 0.0 0.0 2.0 1.9 0.0 APPENDIX C DATA FOR CARBONATE ANALYSES OF SAND, SILT, AND SILT AND CLAY FRACTIONS (CONTINUED)

Sand Silt and Clay Silt SAMPLE Color % vc % c % m % f % vf % silt % clay % Cal % Dol Total Carb Cal/Dol % Cal % Dol Total Carb Cal/Dol 18.0 brown 16.0 13.4 8.8 10.1 23.4 4.6 5.1 0.4 9.2 9.7 0.1 0.0 4.6 4.5 0.0 56.0 brown 19.9 18.3 10.5 0.7 5.4 0.3 3.3 0.3 3.3 3.6 0.1 0.0 0.3 0.3 0.0 66.0 brown 15.1 12.1 8.0 7.4 8.7 1.3 0.0 0.0 0.9 0.9 0.0 0.0 1.3 1.3 0.0 73.0 brown 0.6 3.0 0.0 3.6 3.6 0.0 0.0 0.6 0.6 0.0 Mean 17.0 13.7 8.4 6.1 11.3 1.9 4.0 0.2 5.6 5.8 0.0 0.1 1.8 1.8 0.1 Variance 3.3 8.4 4.3 13.6 55.0 2.5 18.5 0.1 22.4 24.5 0.0 0.1 2.4 2.3 0.0 n= 5 5 5 5 5 6 6 6 6 6 6 6 6 6 6 14.0 pink 25.7 22.8 15.0 13.0 11.3 2.6 4.5 2.0 5.2 7.1 0.4 1.2 1.4 2.6 0.9 19.0 pink 22.8 19.8 15.7 11.8 12.4 3.6 4.8 2.9 5.5 8.4 0.5 2.2 1.4 3.6 1.5 20.0 pink 27.2 21.9 14.3 11.3 11.4 3.3 4.4 3.4 4.3 7.7 0.8 1.9 1.5 3.3 1.2 21.0 pink 20.9 20.7 13.5 10.4 11.1 2.7 4.2 2.0 4.9 6.9 0.4 1.3 1.5 2.7 0.9 22.0 pink 22.1 20.6 11.9 8.2 8.7 2.8 3.8 1.3 5.3 6.6 0.2 1.4 1.5 2.8 0.9 120 23.0 pink 23.7 20.9 12.8 9.4 10.5 2.0 4.2 1.3 4.9 6.2 0.3 0.9 1.2 2.0 0.7 24.0 pink 19.3 20.3 11.8 8.4 9.0 3.0 3.0 1.3 4.7 6.0 0.3 1.6 1.4 3.0 1.1 25.0 pink 25.9 18.0 12.5 8.8 9.3 3.3 3.0 1.1 5.3 6.3 0.2 1.2 2.1 3.3 0.6 26.0 pink 21.2 22.0 13.2 9.8 10.7 3.5 3.8 1.8 5.5 7.3 0.3 1.4 2.2 3.5 0.6 27.0 pink 22.4 20.6 14.3 10.0 11.2 3.1 4.5 2.3 5.3 7.6 0.4 1.2 1.9 3.1 0.6 28.0 pink 29.6 24.4 15.8 11.6 12.9 3.6 4.6 1.9 6.3 8.2 0.3 1.4 2.2 3.6 0.7 29.0 pink 21.6 20.2 12.9 10.1 11.9 4.1 2.9 1.1 5.9 7.0 0.2 2.2 2.0 4.1 1.1 34.0 pink 23.8 20.6 12.4 9.2 10.1 2.6 2.7 0.7 4.6 5.3 0.2 0.3 2.3 2.6 0.1 35.0 pink 23.0 21.5 13.9 10.9 11.5 2.3 3.5 1.1 4.8 5.8 0.2 0.3 2.0 2.3 0.1 36.0 pink 23.1 20.9 11.7 11.3 11.9 3.4 3.0 1.2 5.2 6.4 0.2 1.9 1.5 3.4 1.3 37.0 pink 24.5 22.3 14.2 11.2 12.1 1.6 5.1 1.4 5.3 6.7 0.3 0.6 1.1 1.6 0.5 38.0 pink 26.2 21.4 14.4 10.6 11.8 3.2 3.7 1.7 5.2 6.9 0.3 1.9 1.2 3.2 1.6 39.0 pink 22.5 20.4 14.1 10.7 10.8 1.9 4.6 1.8 4.7 6.5 0.4 0.2 1.7 1.9 0.1 40.0 pink 17.6 19.0 9.4 5.9 7.0 1.3 2.8 0.0 4.1 4.1 0.0 0.0 1.3 1.3 0.0 41.0 pink 20.7 45.6 20.9 11.3 11.3 0.3 4.3 0.0 4.5 4.6 0.0 0.0 0.3 0.3 0.0 42.0 pink 23.1 22.8 13.3 10.4 12.2 2.3 4.4 1.9 4.8 6.7 0.4 0.3 2.1 2.3 0.1 43.0 pink 22.7 21.5 13.9 12.1 11.6 2.1 4.3 1.8 4.6 6.4 0.4 0.0 2.1 2.0 0.0 44.0 pink 20.5 19.8 11.7 7.2 7.5 4.4 2.2 1.8 4.8 6.6 0.4 0.5 3.9 4.4 0.1 49.0 pink 36.4 29.7 19.4 14.2 17.2 3.8 5.2 3.4 5.6 9.0 0.6 1.5 2.3 3.8 0.7 53.0 pink 27.6 22.6 11.3 8.1 9.5 2.2 3.6 0.0 5.8 5.8 0.0 0.6 1.6 2.2 0.4 59.0 pink 32.4 26.9 14.2 9.6 11.3 3.6 0.3 3.3 3.6 0.1 60.0 pink 29.4 24.0 17.2 13.9 13.8 2.4 10.9 3.4 9.8 13.3 0.4 1.3 1.1 2.4 1.3 61.0 pink 21.6 21.1 12.5 7.5 8.3 13.0 0.0 0.9 4.3 5.2 0.2 10.0 3.1 13.0 3.2 62.0 pink 24.9 30.1 17.5 12.7 13.0 3.9 0.8 0.2 4.5 4.7 0.1 2.2 1.6 3.9 1.4 65.0 pink 9.1 6.9 4.2 4.2 5.5 1.3 0.0 0.0 0.0 0.0 0.0 0.0 0.3 0.3 0.0 67.0 pink 24.8 24.4 11.2 8.0 8.9 3.4 2.7 0.9 5.2 6.1 0.2 0.8 2.5 3.4 0.3 APPENDIX C DATA FOR CARBONATE ANALYSES OF SAND, SILT, AND SILT AND CLAY FRACTIONS (CONTINUED)

Sand Silt and Clay Silt SAMPLE Color % vc % c % m % f % vf % silt % clay % Cal % Dol Total Carb Cal/Dol % Cal % Dol Total Carb Cal/Dol 71.0 pink 30.1 28.4 19.4 14.2 14.8 5.4 6.6 0.0 12.0 12.0 0.0 2.9 2.5 5.4 1.2 72.0 pink 0.6 3.9 0.0 4.5 4.5 0.0 0.0 0.3 0.3 0.0 Mean 23.9 22.6 13.8 10.2 11.0 3.1 3.8 1.4 5.2 6.5 0.3 1.3 1.7 3.1 0.7 Variance 22.9 33.4 9.5 5.3 5.2 17.5 16.2 1.5 15.7 21.3 0.0 12.1 1.3 19.0 1.3 n= 32 32 32 32 32 33 33 33 33 33 33 33 33 33 33 30.0 pink-brown 14.3 17.0 12.4 11.5 14.1 0.9 4.8 1.1 4.6 5.7 0.2 0.0 0.9 0.9 0.0 31.0 pink-brown 14.7 15.6 11.8 8.8 10.9 2.4 1.9 0.9 3.3 4.3 0.3 1.6 0.8 2.4 2.0 32.0 pink-brown 18.2 16.2 10.6 7.8 9.9 1.3 2.7 0.6 3.4 4.0 0.2 0.0 1.3 1.2 0.0 33.0 pink-brown 16.4 16.9 10.1 9.2 12.4 1.1 4.0 0.9 4.2 5.1 0.2 0.0 1.1 1.1 0.0 48.0 pink-brown 23.8 25.5 11.9 7.0 8.4 0.3 0.0 0.0 0.3 0.3 0.0 0.0 0.3 0.3 0.0 55.0 pink-brown 8.3 5.8 3.0 3.6 5.1 1.1 0.0 0.0 0.0 0.0 0.0 0.4 0.7 1.1 0.6 58.0 pink-brown 31.7 25.8 16.0 12.8 15.0 3.8 4.3 3.0 5.1 8.1 0.6 2.6 1.1 3.8 2.3 121 64.0 pink-brown 12.0 7.2 5.0 4.5 7.5 0.0 0.3 0.0 0.3 0.3 0.0 0.0 0.3 0.3 0.0 Mean 17.4 16.3 10.1 8.2 10.4 1.4 2.3 0.8 2.6 3.5 0.2 0.6 0.8 1.4 0.6 Variance 53.7 52.9 17.6 10.1 11.3 1.4 4.1 1.0 4.5 8.9 0.0 1.0 0.1 1.4 0.9 n= 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8

APPENDIX D CRYSTALLINE AND CLASTIC DATA

Sample Color Pink Shale Gray Shale SS & SLTST Other Rd Quartz Angle Quartz LT IG DK IG LT Meta DK Meta Total Clasts Total Xtal Total % Clast % Xtal ratioX/C 1 gray 0 0 24 3 28 23 101 19 1 9 55 153 208 26 74 2.78 2 gray 0 5 184 1 45 92 128 127 0 11 235 358 593 40 60 1.52 3 gray 1 1 233 2 41 39 129 103 1 10 278 282 560 50 50 1.01 4 gray 0 4 150 0 22 32 74 61 0 4 176 171 347 51 49 0.97 5 gray 0 2 130 0 25 16 47 44 0 12 157 119 276 57 43 0.76 7 gray 3 16 320 2 40 41 91 50 0 3 381 185 566 67 33 0.49 8 gray 0 11 379 8 39 43 91 52 1 9 437 196 633 69 31 0.45 9 gray 0 10 241 5 8 40 84 30 0 6 264 160 424 62 38 0.61 122 10 gray 0 10 495 11 54 35 76 64 0 9 570 184 754 76 24 0.32 11 gray 0 6 230 0 19 11 36 17 1 3 255 68 323 79 21 0.27 12 gray 0 5 227 1 16 21 27 16 0 3 249 67 316 79 21 0.27 13 gray 0 1 245 3 38 14 11 12 0 1 287 38 325 88 12 0.13 15 gray 3 7 232 0 22 22 15 13 0 1 264 51 315 84 16 0.19 16 gray 0 8 247 0 22 23 17 4 0 0 277 44 321 86 14 0.16 45 gray 3 19 246 0 24 5 6 9 0 0 292 20 312 94 6 0.07 46 gray 0 20 266 2 14 18 5 0 0 0 302 23 325 93 7 0.08 47 gray 0 11 261 1 15 20 5 1 0 0 288 26 314 92 8 0.09 50 gray 0 22 177 0 15 10 5 7 0 0 214 22 236 91 9 0.10 51 gray 0 27 248 3 20 5 5 3 0 0 298 13 311 96 4 0.04 52 gray 0 24 210 4 16 13 20 28 0 0 254 61 315 81 19 0.24 54 gray 0 15 252 7 17 12 5 3 0 1 291 21 312 93 7 0.07 55 gray 4 10 242 1 21 25 4 2 0 0 278 31 309 90 10 0.11 57 gray 1 32 269 0 8 11 11 3 0 2 310 27 337 92 8 0.09 63 gray 0 16 232 2 19 15 5 4 0 0 269 24 293 92 8 0.09 68 gray 1 26 237 8 14 20 11 1 0 0 286 32 318 90 10 0.11 69 gray 0 24 261 1 13 4 0 7 0 0 299 11 310 96 4 0.04 70 gray 0 21 269 1 15 4 1 2 0 0 306 7 313 98 2 0.02 Mean 1 13 241 2 23 23 37 25 0 3 280 89 369 78 22 0.41 Variance 1 83 6523 9 140 329 1770 1062 0 17 7999 8435 17254 368 368 0.36 n= 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27

14 pink 0 6 301 1 14 18 5 4 0 1 322 28 350 92 8 0.09 19 pink 0 19 270 0 12 14 13 5 0 0 301 32 333 90 10 0.11 20 pink 0 13 190 0 13 26 15 11 0 0 216 52 268 81 19 0.24 21 pink 2 26 241 1 16 18 12 10 0 2 286 42 328 87 13 0.15 22 pink 0 17 249 5 19 15 20 13 0 2 290 50 340 85 15 0.17 23 pink 5 22 248 4 11 20 10 16 0 0 290 46 336 86 14 0.16 24 pink 5 13 249 3 23 13 6 8 0 2 293 29 322 91 9 0.10 25 pink 5 23 213 3 15 23 27 11 0 1 259 62 321 81 19 0.24 26 pink 5 18 236 2 36 13 8 5 1 0 297 27 324 92 8 0.09 27 pink 8 20 238 0 13 12 6 15 0 0 279 33 312 89 11 0.12 28 pink 11 22 239 1 15 13 8 7 0 0 288 28 316 91 9 0.10 APPENDIX D CRYSTALLINE AND CLASTIC DATA (CONTINUED)

Sample Color Pink Shale Gray Shale SS & SLTST Other Rd Quartz Angle Quartz LT IG DK IG LT Meta DK Meta Total Clasts Total Xtal Total % Clast % Xtal ratioX/C 29 pink 7 35 199 1 15 32 30 9 0 1 257 72 329 78 22 0.28 34 pink 4 18 239 0 17 15 12 7 0 0 278 34 312 89 11 0.12 35 pink 10 15 212 1 21 18 9 6 0 0 259 33 292 89 11 0.13 36 pink 16 16 234 1 10 9 8 4 0 0 277 21 298 93 7 0.08 37 pink 1 24 262 1 10 14 13 5 0 0 298 32 330 90 10 0.11 38 pink 4 16 267 1 17 8 10 7 0 0 305 25 330 92 8 0.08 39 pink 4 16 240 1 12 6 3 13 0 0 273 22 295 93 7 0.08 40 pink 3 20 245 4 18 16 12 5 0 2 290 35 325 89 11 0.12 41 pink 2 40 214 2 18 19 24 8 0 1 276 52 328 84 16 0.19 42 pink 1 23 235 2 21 14 11 3 0 0 282 28 310 91 9 0.10 43 pink 1 18 229 1 11 6 7 0 0 0 260 13 273 95 5 0.05 44 pink 2 30 228 1 14 12 4 5 0 1 275 22 297 93 7 0.08 49 pink 0 24 228 0 12 9 6 2 0 0 264 17 281 94 6 0.06 53 pink 1 24 270 11 9 13 8 3 1 0 315 25 340 93 7 0.08 59 pink 20 32 220 4 18 7 10 1 0 0 294 18 312 94 6 0.06 60 pink 8 6 202 0 4 4 0 0 0 0 220 4 224 98 2 0.02 61 pink 1 22 231 5 21 13 11 13 0 2 280 39 319 88 12 0.14 62 pink 0 24 247 1 19 9 9 8 0 0 291 26 317 92 8 0.09 123 65 pink 1 32 251 2 16 5 3 0 0 0 302 8 310 97 3 0.03 67 pink 1 33 201 1 17 28 5 3 0 0 253 36 289 88 12 0.14 71 pink 1 25 218 0 12 20 11 2 0 0 256 33 289 89 11 0.13 Mean 4 22 236 2 16 14 11 7 0 0 279 32 311 90 10 0.12 Variance 23 59 561 5 31 44 45 20 0 1 554 215 657 21 21 0.00 n= 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32

6 brown 0 9 374 2 73 53 159 73 0 5 458 290 748 61 39 0.63 17 brown 0 11 242 0 19 20 16 10 0 0 272 46 318 86 14 0.17 18 brown 3 20 228 0 20 26 9 1 0 0 271 36 307 88 12 0.13 56 brown 0 20 257 4 16 23 7 1 0 0 297 31 328 91 9 0.10 66 brown 2 17 252 7 22 13 3 2 0 0 300 18 318 94 6 0.06 Mean 1 15 271 3 30 27 39 17 0 1 320 84 404 84 16 0.22 Variance 2 26 3464 9 583 235 4537 980 0 5 6169 13337 37078 172 172 0.05 n= 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

30 pink-brown 12 19 231 0 22 13 4 2 0 0 284 19 303 94 6 0.07 31 pink-brown 11 15 235 3 12 13 14 5 0 0 276 32 308 90 10 0.12 32 pink-brown 11 24 239 1 14 17 13 4 0 0 289 34 323 89 11 0.12 33 pink-brown 11 16 250 2 12 16 10 2 0 0 291 28 319 91 9 0.10 48 pink-brown 0 18 252 2 18 10 2 4 0 0 290 16 306 95 5 0.06 58 pink-brown 0 22 222 0 17 12 1 1 0 0 261 14 275 95 5 0.05 64 pink-brown 1 8 198 1 25 27 3 5 0 0 233 35 268 87 13 0.15 Mean 7 17 232 1 17 15 7 3 0 0 275 25 300 92 8 0.09 Variance 34 27 340 1 25 32 30 3 0 0 453 79 441 9 9 0.00 n= 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7.00

APPENDIX E CHEMICAL ANALYSES OF SAND FRACTION

Analyte Ag Al As As Ba Be Bi Ca Cd Co Cr Cu Fe K La Li Mg Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 0.01 3 3 1 0.5 5 0.01 1 1 1 0.5 0.01 0.01 0.5 1 0.01 Units PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM 1_SD <2 26500 10 10 193 0.8 <5 28900 <1 58 21 62.9 28800 8300 17.2 16 6700 2_SD <2 33200 9 9 235 0.9 <5 22800 <1 52 24 139 28300 10100 18 23 5700 3_SD <2 33300 12 12 220 1 <5 33100 <1 46 25 41.9 36100 10300 19.4 23 9600 4_SD <2 25700 12 12 188 0.7 <5 24000 <1 81 19 33.3 27500 8300 14.9 16 6500 5_SD <2 24000 6 6 188 0.7 <5 18800 <1 179 22 56.2 18700 8000 14.2 14 5200 7_SD <2 37000 8 8 235 1 <5 31400 <1 57 25 37.3 31300 11500 19.5 28 8900 124 8_SD <2 37500 8 8 263 1 <5 33000 <1 33 25 33.4 29900 12000 21.8 26 9600 9_SD <2 27000 6 6 207 0.8 <5 24300 <1 80 22 40.5 21300 9000 17.1 17 6000 10_SD <2 34000 9 9 241 0.9 <5 30700 <1 31 24 37.4 29000 11000 23 22 8600 11_SD <2 36800 11 11 226 1.1 <5 36100 <1 58 27 28.6 37200 11100 20 28 10500 12_SD <2 33200 9 9 221 0.9 <5 27300 <1 45 25 29.2 29300 10200 18.1 24 8100 13_SD <2 37900 6 6 253 1 <5 31700 <1 64 27 34 29200 11900 20.6 27 9200 15_SD <2 42800 16 16 268 1.3 <5 59500 <1 43 34 35.2 46300 14500 24.3 40 15200 16_SD <2 51700 15 15 302 1.4 <5 58100 <1 31 39 36.6 44500 16000 25.6 41 16000 45_SD <2 54900 9 9 372 1.3 <5 40600 <1 28 40 49.2 30300 17900 23.4 35 15300 46_SD <2 50800 9 9 374 1.2 <5 43800 <1 42 42 44.2 28900 17700 21.4 33 15600 47_SD <2 58600 17 17 341 1.7 <5 57000 <1 34 43 61.2 51600 17700 32.8 51 14900 50_SD <2 50000 <3 2 380 1.1 <5 52900 <1 43 32 28.2 24700 17900 18.4 23 17700 51_SD <2 39100 12 12 260 1 <5 31200 <1 61 27 35 36400 12200 22.4 30 9100 52_SD <2 41200 9 9 317 1.1 <5 31300 <1 90 30 33.7 27000 12800 20.2 27 10200 54_SD <2 25500 9 9 204 0.7 <5 19600 <1 61 19 26.3 21000 8500 14 15 5900 57_SD <2 46400 11 11 337 1.1 <5 39300 <1 69 36 33.2 28000 16100 20.9 30 13000 63_SD <2 41500 7 7 312 1.1 <5 33500 <1 67 30 26.3 24000 14300 18.5 27 11700 68_SD <2 42400 8 8 326 1.1 <5 41500 <1 31 33 29.4 28500 14800 23.1 27 14700 69_SD <2 72300 15 15 451 2.2 <5 15300 <1 34 60 34.8 51200 19500 32.9 49 8700 70_SD <2 42200 9 9 299 1.2 <5 20300 <1 26 29 20.9 30200 12600 20.9 29 7400 mean b-d 40211.54 10.08 9.77 277.42 1.09 b-d 34076.92 b-d 55.54 30.00 41.07 31507.69 12853.85 20.87 27.73 10384.62 n= 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26

6_SD <2 39000 12 268 1.1 <5 14400 <1 38 30 37.1 35700 11800 20.7 30 5100 17_SD <2 41400 16 283 1.1 <5 27100 <1 36 29 72.3 41100 11000 21.4 29 6600 18_SD <2 47200 25 332 1.3 <5 32600 <1 23 35 25.6 43800 13500 28 40 5700 56_SD <2 52300 7 438 1.3 <5 4900 <1 42 38 24.3 28300 19000 24.3 33 5300 66_SD <2 47400 15 406 1.4 <5 5000 <1 29 37 38.3 37100 14700 30 33 4500 mean 45460.00 15.00 345.40 1.24 b-d 16800.00 b-d 33.60 33.80 39.52 37200.00 14000.00 24.88 33.00 5440.00 n= 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

14_SD <2 53600 11 11 363 1.5 <5 40500 <1 30 42 32.5 31000 18600 23.7 35 14400 19_SD <2 53300 8 8 365 1.3 <5 41900 <1 40 41 42.3 30700 18600 23.3 35 14400 APPENDIX E CHEMICAL ANALYSES OF SAND FRACTION (CONTINUED)

Analyte Ag Al As As Ba Be Bi Ca Cd Co Cr Cu Fe K La Li Mg Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 0.01 3 3 1 0.5 5 0.01 1 1 1 0.5 0.01 0.01 0.5 1 0.01 Units PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM 20_SD <2 46700 10 10 319 1.2 <5 35600 <1 40 35 26.9 28200 15400 21.3 31 12400 21_SD <2 46100 8 8 335 1.2 <5 34800 <1 41 36 33.4 29200 15500 21.3 32 11800 22_SD <2 46700 10 10 301 1.3 <5 33200 <1 33 34 29.5 30900 15100 23.7 34 11700 23_SD <2 39300 5 5 282 1 <5 31000 <1 59 29 38.8 24800 13200 18.7 26 10200 24_SD <2 41200 8 8 283 1.1 <5 31200 <1 31 31 28.1 28500 13600 20.3 29 10900 25_SD <2 38400 7 7 285 1 <5 30000 <1 63 32 34.6 25700 12900 18.9 27 10000 26_SD <2 48900 12 12 330 1.3 <5 37100 <1 27 36 34 31400 16600 23.7 34 13000 27_SD <2 53800 8 8 350 1.4 <5 37800 <1 36 43 44.6 32600 18600 23.9 37 13900 28_SD <2 50500 6 6 352 1.3 <5 45200 <1 26 36 47 29900 17800 21.9 32 15200 29_SD <2 47700 6 6 325 1.2 <5 42200 <1 42 34 30.5 27700 16800 21.7 30 14500 34_SD <2 44200 7 7 314 1.1 <5 33400 <1 33 31 25.7 26100 15200 20.8 31 11400 35_SD <2 50700 7 7 381 1.2 <5 42600 <1 43 38 39.1 28300 18100 22.2 33 15300 36_SD <2 43900 6 6 342 1.1 <5 41900 <1 36 31 37.5 24500 15700 19.4 28 14000 37_SD <2 50300 7 7 356 1.3 <5 39600 <1 25 39 38.5 30100 17500 22.8 34 14300 38_SD <2 48300 8 8 338 1.2 <5 39100 <1 39 35 35.8 28400 16900 21.1 31 13600 39_SD <2 46300 10 10 313 1.2 <5 37400 <1 31 34 37.9 28800 16000 22.3 33 12600 125 40_SD <2 40200 7 7 273 1.2 <5 30400 <1 49 28 37.1 30500 12200 22.8 32 9300 41_SD <2 36600 10 10 269 1.1 <5 25100 <1 34 26 43.3 30100 12100 21.5 26 8400 42_SD <2 50200 9 9 365 1.4 <5 38900 <1 42 40 39.4 29900 17900 24.2 36 14000 43_SD <2 47100 9 9 322 1.2 <5 45100 <1 26 35 44.9 29100 16800 25 33 15100 44_SD <2 39400 8 8 328 1 <5 37100 <1 52 28 29.8 24500 14400 18.8 24 13100 49_SD <2 41000 4 4 336 1 <5 39700 <1 155 28 66.7 22400 14700 17.1 23 12800 59_SD <2 36500 21 21 276 1 <5 22200 <1 56 26 38 37500 12400 19.9 23 7600 60_SD <2 58200 9 9 379 1.4 <5 41100 <1 26 39 83 32700 19000 27.6 38 15400 61_SD <2 32400 10 10 235 1 <5 24400 <1 65 25 29.1 26700 10500 18.1 23 7500 62_SD <2 53300 11 11 372 1.5 <5 36700 <1 25 41 42.2 38000 17300 28 43 15000 65_SD <2 58300 7 7 415 1.5 <5 5100 <1 48 45 43.6 45700 19200 27.4 34 6800 67_SD <2 38100 7 7 290 1.1 <5 29000 <1 46 29 33.7 26800 12300 21.7 28 10800 71_SD <2 47400 <3 2 400 1 <5 59400 <1 31 30 33.2 23100 18800 18.4 22 22500 72_SD <2 42500 15 15 307 1.2 <5 31400 <1 28 30 26.1 30600 14600 25.1 29 11600 means 45971.88 8.74 8.53 328.16 1.20 b-d 35628.13 b-d 42.44 33.97 38.34 29512.50 15759.38 22.08 30.81 12609.38 n= 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32

30_SD <2 52300 9 409 1.4 <5 30700 <1 28 41 34.8 34500 18400 25.9 34 9200 31_SD <2 45400 6 366 1.2 <5 26300 <1 64 35 53 26900 16000 21.7 30 7900 32_SD <2 50800 10 426 1.4 <5 26400 <1 25 39 62.5 31000 17400 26.5 34 9000 33_SD <2 47000 7 367 1.2 <5 28100 <1 40 35 33.6 28000 16000 24.2 33 8800 48_SD <2 42400 16 354 1.2 <5 3900 <1 50 33 47.1 41100 13000 25.8 32 3700 55_SD <2 47200 9 358 1.3 <5 18900 <1 43 36 35.1 30300 15700 25.8 35 7800 58_SD <2 57400 5 448 1.4 <5 45000 <1 23 40 28.4 30600 21000 24.8 27 16200 64_SD <2 52600 6 503 1.3 <5 6700 <1 44 37 30.9 28200 20200 22.9 24 6000 mean 49387.50 8.50 b-d 403.88 1.30 b-d 23250.00 b-d 39.63 37.00 40.68 31325.00 17212.50 24.70 31.13 8575.00 n= 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

DUP-1_SD <2 25100 10 195 0.8 <5 27700 <1 59 23 69.4 29300 8200 17.3 16 6700 DUP-15_SD <2 41800 15 245 1.2 <5 54000 <1 39 32 33.7 42200 13200 23.4 36 14000 DUP-69_SD <2 73200 15 445 2.2 <5 15200 <1 32 59 38.1 53500 20100 34.2 49 8800 DUP-23_SD <2 39000 8 283 1 <5 30700 <1 59 28 40.3 25300 13500 18.9 26 10400 DUP-39_SD <2 49100 10 318 1.3 <5 38100 <1 32 36 39.9 30200 17100 22.5 36 13200 DUP-67_SD <2 40600 7 297 1.1 <5 31400 <1 49 28 34.7 29200 13400 22.7 29 11600

APPENDIX E CHEMICAL ANALYSES OF SAND FRACTION (CONTINUED)

Analyte Mn Mo Na Ni P Pb Sb Sc Sn Sr Ti V W Y Zn Zr Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 1 0.01 1 0.01 2 5 0.5 10 0.5 0.01 2 10 0.5 0.5 0.5 Units PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM 1_SD 568 1 4200 15 600 17 5 4.4 <10 99.8 1200 31 720 14 91.4 70.7 2_SD 486 1 4600 16 400 20 <5 4.9 <10 87 1300 37 530 13.2 96.1 70 3_SD 613 1 4700 18 500 20 6 5.3 <10 102 1400 38 510 14.7 99.4 74.3 4_SD 472 1 4200 13 400 25 5 3.9 10 77.5 1100 28 480 11.4 65.8 56.3 5_SD 335 2 4400 12 300 18 <5 3.4 <10 73.2 1100 25 680 9.9 73.8 52.2 7_SD 564 1 4900 16 500 31 5 5.5 10 98.6 1400 40 470 13.5 81.4 70.8 8_SD 561 1 5600 17 500 20 5 5.4 <10 103 1400 40 350 14.9 89.3 83.1 9_SD 386 1 4700 13 400 15 <5 3.8 <10 86 1200 29 430 11.4 83.7 63.7 10_SD 528 1 5400 16 500 21 6 4.8 <10 98.9 1400 36 300 14.5 95 85.1 11_SD 617 1 4400 19 500 22 6 5.9 <10 96 1400 44 540 15.1 89.2 73.4 12_SD 502 <1 4800 15 400 18 5 4.8 <10 90 1300 37 370 13 74.7 69.5 13_SD 511 2 5200 18 500 19 6 5.6 <10 97.8 1400 42 620 14.1 196 73.1

126 15_SD 781 2 5400 24 700 19 8 7.4 <10 146 1300 56 420 18.9 109 86 16_SD 781 2 5900 26 700 27 9 7.9 <10 149 1600 62 270 19.6 104 98.3 45_SD 495 2 6900 24 500 17 6 8.1 <10 136 1800 61 260 16.2 87.8 78.6 46_SD 469 3 7200 25 500 19 6 7.3 <10 142 1700 60 410 15 93.6 76.8 47_SD 877 2 6100 28 800 43 8 9.1 <10 155 2000 71 270 22.3 146 116 50_SD 670 <1 10100 17 500 12 6 6.6 <10 187 2000 56 410 16.3 56.3 65.1 51_SD 650 1 5300 19 500 26 6 5.7 <10 107 1600 44 490 15.2 90.3 78.8 52_SD 501 2 6400 18 400 21 7 5.9 <10 117 1500 45 780 14.1 84.8 70.2 54_SD 379 1 4700 12 300 14 <5 3.6 <10 79.4 1200 27 430 10.4 64.1 55.7 57_SD 506 2 7400 21 500 17 5 6.9 <10 133 1900 55 640 16.1 81.9 81.8 63_SD 459 2 6100 17 400 15 5 6.2 <10 125 1500 47 650 13 68.8 63.4 68_SD 547 1 6200 20 500 15 5 5.9 <10 133 1500 47 280 14.5 78.8 71.4 69_SD 629 <1 2700 32 500 28 10 13 <10 113 2500 96 220 19.3 143 100 70_SD 388 1 4800 18 400 20 6 6.2 <10 93.5 1500 47 240 13.9 87.3 76.8 mean 549.04 1.48 5473.08 18.81 488.46 20.73 6.18 6.06 10.00 112.53 1507.69 46.19 452.69 14.79 93.52 75.43 n= 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26

6_SD 556 1 4800 20 500 19 6 6.1 <10 76.9 1500 48 380 15.3 99.1 81.3 17_SD 477 <1 6200 21 600 29 6 6.7 <10 117 1600 53 280 15.5 106 67.9 18_SD 732 1 4700 22 600 31 8 7.3 <10 107 1700 58 160 18.7 111 96 56_SD 1060 <1 7700 25 600 22 6 7 <10 109 2000 60 240 16.6 77.5 88.3 66_SD 960 1 5500 29 600 22 7 7.1 <10 76.8 1700 55 170 18.3 104 104 mean 757.00 1.00 5780.00 23.40 580.00 24.60 6.60 6.84 97.34 1700.00 54.80 246.00 16.88 99.52 87.50 n= 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

14_SD 562 3 7100 25 500 17 8 8.1 <10 139 1900 66 270 16.4 95.6 79.9 19_SD 568 3 7500 25 500 28 7 8 <10 143 1900 67 340 16.9 79.5 81.7 20_SD 528 2 6200 23 500 18 6 6.8 <10 123 1600 56 340 15.3 77.9 74.3 21_SD 510 2 6300 21 500 17 6 6.7 <10 123 1600 55 370 14.6 83.4 74.7 22_SD 547 2 5700 20 500 18 7 7 <10 109 1700 56 290 16 93.5 82.6 23_SD 487 2 6200 16 400 15 6 5.8 <10 112 1500 44 490 13.8 63 68.4 24_SD 521 1 5800 17 500 17 7 6 <10 108 1400 47 300 14.2 79.4 72.2 25_SD 472 1 5700 19 400 16 6 5.8 <10 106 1400 46 530 13.7 70.5 69.3 26_SD 556 2 6600 21 500 17 6 7.3 <10 130 1700 59 250 16.2 93.2 81.5 APPENDIX E CHEMICAL ANALYSES OF SAND FRACTION (CONTINUED)

Analyte Mn Mo Na Ni P Pb Sb Sc Sn Sr Ti V W Y Zn Zr Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 1 0.01 1 0.01 2 5 0.5 10 0.5 0.01 2 10 0.5 0.5 0.5 Units PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM PPM 27_SD 550 3 6800 25 500 19 5 8.2 <10 134 1800 67 330 16.4 114 78.5 28_SD 573 2 7200 21 500 18 6 7.5 <10 147 1700 59 240 16.3 76.5 70.5 29_SD 536 2 7000 20 500 17 6 6.9 <10 145 1700 56 380 14.7 77.2 71.2 34_SD 493 2 6500 22 500 15 <5 6.2 <10 123 1600 51 320 14.8 83.4 70.8 35_SD 528 2 7600 23 500 17 6 7.5 <10 147 1900 61 350 16.3 81.2 77 36_SD 480 2 7000 20 500 22 5 6.2 <10 143 1600 49 310 14.2 71.2 65.6 37_SD 548 2 6800 24 500 18 6 7.6 <10 138 1800 64 200 16.3 81.8 78.8 38_SD 522 2 7200 19 500 18 6 7.1 <10 141 1700 55 400 15.3 78.8 71 39_SD 521 2 6300 20 500 17 7 7 <10 122 1700 57 290 15 90.2 74.2 40_SD 540 1 4800 18 500 18 6 6.2 <10 95.9 1400 45 380 15 98.4 81.1 41_SD 500 1 5400 18 500 20 6 5.5 <10 95.4 1300 40 310 14 122 74.5 42_SD 575 2 7300 24 600 18 8 7.8 <10 137 1700 64 370 16.8 79.8 78.7 43_SD 542 2 7100 20 600 20 7 6.9 <10 139 1600 58 230 16.7 98.5 79.8 44_SD 471 1 6900 18 500 16 5 5.6 <10 137 1300 43 470 13.4 75.4 60.9

127 49_SD 499 2 8000 17 400 22 5 5.7 <10 155 1700 48 470 13.6 60.6 60.4 59_SD 383 1 5600 25 500 18 7 5.2 <10 102 1400 41 360 14 87.5 73.8 60_SD 600 2 7000 27 600 18 7 8.7 <10 142 1800 66 190 18 91.8 81 61_SD 459 1 4600 18 400 16 5 4.9 <10 92.2 1200 38 490 12.4 70.4 62.5 62_SD 675 1 5800 24 600 28 7 8.3 <10 122 1800 65 170 18.1 107 95.6 65_SD 805 2 7400 28 900 19 8 8.7 <10 109 2200 76 360 21.5 99.4 97.2 67_SD 495 1 5300 16 500 26 7 5.7 <10 106 1200 42 400 14.2 119 69.1 71_SD 658 <1 9900 16 600 13 5 6.3 <10 199 1800 53 290 15.7 50.6 61.8 72_SD 528 1 6100 20 500 17 <5 6.3 <10 119 1400 50 300 15.2 82.6 71.8 means 538.50 1.77 6584.38 20.94 515.63 18.53 6.30 6.80 b-d 127.61 1625.00 54.50 337.19 15.47 85.42 74.70 n= 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32

30_SD 512 <1 7300 24 600 20 7 7.9 <10 139 1900 68 220 17.8 79.2 84.6 31_SD 388 <1 6900 26 500 20 6 6.5 <10 128 1600 55 410 14.6 81.6 72.3 32_SD 420 <1 6900 35 500 19 7 7.3 <10 128 1800 63 180 16.5 81.7 86.1 33_SD 322 <1 6400 22 500 16 7 6.9 <10 124 1600 57 350 15.9 73.6 78.5 48_SD 706 1 5000 27 700 25 7 6.7 <10 75 1700 55 350 17.9 115 86.7 55_SD 390 1 6000 21 500 18 6 7 <10 101 1800 58 340 15.1 73.4 93.9 58_SD 630 <1 9700 23 700 12 7 8 <10 185 2300 73 150 18.7 66.4 82.7 64_SD 1110 1 9700 29 700 18 7 6.9 <10 146 2100 60 270 16.8 74.6 79.9 mean 559.75 1.00 7237.50 25.88 587.50 18.50 6.75 7.15 b-d 128.25 1850.00 61.13 283.75 16.66 80.69 83.09 n= 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

DUP-1_SD 564 1 4200 16 700 18 5 4.5 <10 102 1000 32 650 14.2 92.8 68.9 DUP-15_SD 779 2 4800 23 600 18 7 6.8 <10 136 1300 51 380 17.5 98.9 82.6 DUP-69_SD 626 1 2700 32 500 27 8 12.8 <10 119 2400 96 210 19.4 136 101 DUP-23_SD 481 1 6100 15 400 16 5 5.7 <10 113 1400 45 470 13.3 63.6 65.9 DUP-39_SD 539 2 6600 22 500 20 7 7.1 <10 132 1500 56 300 14.9 97.6 73.7 DUP-67_SD 516 1 5800 16 500 28 5 5.9 <10 117 1300 44 420 14.7 123 73.5

APPENDIX F CHEMICAL ANALYSES OF SILT AND CLAY FRACTION AND SOURCE ROCKS

Analyte Ag Al Al As Ba Be Bi Ca Ca Cd Co Cr Cu Fe Fe K K La Li Mg Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 0.01 3 1 0.5 5 0.01 1 1 1 0.5 0.01 0.01 0.5 1 0.01 Units PPM % PPM PPM PPM PPM PPM % PPM PPM PPM PPM PPM % PPM % PPM PPM PPM % 1 <2 3.93 39300 14 261 1.1 <5 1.68 16800 <1 9 34 44.3 3.34 33400 1.23 12300 28.2 33 0.75 2 <2 4.65 46500 15 337 1.3 <5 1.51 15100 <1 11 47 53.9 3.7 37000 1.49 14900 33.6 41 0.83 3 <2 4.92 49200 10 317 1.3 <5 1.43 14300 <1 10 48 53.1 3.34 33400 1.53 15300 29.1 44 0.8 4 <2 4.7 47000 10 313 1.3 <5 1.38 13800 <1 10 43 48.4 3.3 33000 1.49 14900 30.5 42 0.78 5 <2 4.09 40900 12 274 1 <5 1.47 14700 <1 8 37 41.8 3.2 32000 1.32 13200 31.7 35 0.74 7 <2 6.88 68800 10 413 1.8 <5 1.36 13600 <1 14 55 52.2 3.9 39000 2.15 21500 36 71 0.94 8 <2 3.88 38800 10 269 1 <5 1.46 14600 <1 8 38 86.1 3.03 30300 1.25 12500 30.3 33 0.72 128 9 <2 4.21 42100 13 285 1.1 <5 1.46 14600 <1 9 41 91.4 3.3 33000 1.36 13600 33.9 36 0.76 10 2 4 40000 11 266 1 <5 1.46 14600 <1 8 39 73 3.23 32300 1.28 12800 33.5 34 0.75 11 <2 4.77 47700 9 313 1.3 <5 1.31 13100 <1 10 43 42.9 3.18 31800 1.51 15100 28.7 43 0.77 12 <2 4.73 47300 11 314 1.3 <5 1.44 14400 <1 9 44 49.7 3.36 33600 1.51 15100 30.5 42 0.84 13 <2 6.32 63200 12 399 1.7 <5 1.58 15800 <1 13 56 68.6 3.83 38300 2.05 20500 34.2 61 1 15 <2 6.98 69800 11 435 1.8 <5 1.72 17200 <1 14 56 125 3.94 39400 2.3 23000 36.9 68 1.1 16 <2 6.96 69600 15 431 1.9 <5 1.97 19700 <1 15 63 42.6 4.15 41500 2.47 24700 32.7 67 1.24 45 <2 6.24 62400 14 398 1.7 <5 2.09 20900 <1 13 52 30.4 3.86 38600 2.18 21800 32.1 56 1.2 46 <2 6.81 68100 13 423 1.9 <5 2.11 21100 <1 14 59 31.2 4.14 41400 2.44 24400 32 65 1.27 47 <2 5.95 59500 11 360 1.6 <5 1.29 12900 <1 12 50 36.5 3.47 34700 1.84 18400 31.6 62 0.84 50 <2 6.97 69700 7 449 1.9 <5 3.26 32600 <1 14 61 36 4.08 40800 2.61 26100 35.3 56 1.65 51 <2 5.57 55700 11 351 1.5 <5 1.34 13400 <1 11 48 58.1 3.38 33800 1.73 17300 30.6 57 0.82 52 <2 6.2 62000 12 404 1.7 <5 1.79 17900 <1 13 54 38.9 3.82 38200 2.07 20700 32 58 1.08 54 <2 4.85 48500 11 324 1.3 <5 1.7 17000 <1 9 43 74 3.32 33200 1.58 15800 31 42 0.88 57 <2 6.06 60600 15 396 1.7 <5 1.98 19800 <1 13 56 37.6 3.54 35400 2.08 20800 30.2 56 1.11 63 <2 7 70000 11 452 1.9 <5 2.06 20600 <1 14 59 42 4.08 40800 2.36 23600 34.1 71 1.21 68 <2 6.3 63000 11 421 1.7 <5 2.43 24300 <1 12 54 40.6 3.78 37800 2.16 21600 34.2 59 1.31 69 <2 8.74 87400 6 516 2.3 <5 0.53 5300 <1 11 61 43.9 2.93 29300 2.39 23900 46.2 62 0.69 70 <2 6.98 69800 8 476 2 <5 1.02 10200 <1 12 58 34.2 3.86 38600 2.07 20700 38.6 64 0.88 77 <2 4.38 43800 28 309 1.3 <5 3.72 37200 <1 27 32 42.3 6.2 62000 1.3 13000 24.6 36 0.65 78 <2 3.57 35700 11 237 1 <5 3.01 30100 <1 34 27 24.3 3.04 30400 1.18 11800 22.7 30 1.11 Mean b-d 5.59 55942.86 11.86 362.25 1.51 b-d 1.77 17700.00 b-d 12.75 48.50 51.54 3.65 36535.71 1.82 18189.29 32.32 50.86 0.95 n= 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28

6 <2 4.95 49500 14 392 1.4 <5 0.9 9000 <1 11 46 65.8 3.67 36700 1.56 15600 30.6 44 0.62 17 <2 5.03 50300 25 426 1.6 <5 2.5 25000 <1 17 46 54.8 5.79 57900 1.62 16200 36.5 47 1.35 18 <2 4.58 45800 78 925 1.7 <5 3.19 31900 <1 33 43 97.7 8.75 87500 1.5 15000 36.9 47 1.84 56 <2 6.15 61500 11 431 1.8 <5 1.58 15800 <1 13 55 29.1 3.77 37700 2.02 20200 36.9 56 0.98 66 <2 5.53 55300 13 440 1.7 <5 0.41 4100 <1 10 47 30.5 4.19 41900 1.73 17300 42 47 0.53 Mean b-d 5.25 52480.00 28.20 522.80 1.64 b-d 1.72 17160.00 b-d 16.80 47.40 55.58 5.23 52340.00 1.69 16860.00 36.58 48.20 1.06 n= 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

14 <2 6.84 68400 9 428 1.9 <5 2.53 25300 <1 14 60 40.1 4.11 41100 2.48 24800 30.7 60 1.35 APPENDIX F CHEMICAL ANALYSES OF SILT AND CLAY FRACTION AND SOURCE ROCKS (CONTINUED)

Analyte Ag Al Al As Ba Be Bi Ca Ca Cd Co Cr Cu Fe Fe K K La Li Mg Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 0.01 3 1 0.5 5 0.01 1 1 1 0.5 0.01 0.01 0.5 1 0.01 Units PPM % PPM PPM PPM PPM PPM % PPM PPM PPM PPM PPM % PPM % PPM PPM PPM % 19 <2 6.88 68800 10 435 1.9 <5 2.67 26700 <1 15 64 29.4 4.15 41500 2.5 25000 33.5 60 1.42 20 <2 7.49 74900 11 456 2 <5 2.45 24500 <1 15 56 31.8 4.48 44800 2.41 24100 34.1 67 1.39 21 <2 6.99 69900 12 443 1.9 <5 2.22 22200 <1 15 55 31.2 4.24 42400 2.42 24200 38.5 64 1.3 22 <2 6.54 65400 11 414 1.8 <5 1.87 18700 <1 14 53 32.5 3.98 39800 2.2 22000 38.4 62 1.15 23 <2 6.21 62100 10 400 1.8 <5 2.01 20100 <1 13 53 36.4 3.79 37900 2.13 21300 37 58 1.17 24 <2 6.45 64500 12 414 1.8 <5 1.92 19200 <1 14 57 31.6 3.97 39700 2.18 21800 35.7 60 1.15 25 <2 6.55 65500 14 422 1.8 <5 2.17 21700 <1 14 57 40.7 4.04 40400 2.27 22700 36.5 61 1.25 26 <2 6.79 67900 12 433 1.9 <5 2.13 21300 <1 15 57 36 4.18 41800 2.33 23300 39 62 1.26 27 <2 6.78 67800 9 432 1.9 <5 2.51 25100 <1 15 54 31.8 4.1 41000 2.42 24200 37.4 60 1.36 28 <2 6.61 66100 9 438 1.9 <5 2.68 26800 <1 15 59 42 3.99 39900 2.35 23500 34.2 59 1.43 29 <2 6.82 68200 10 432 1.9 <5 2.64 26400 <1 15 59 33 4.13 41300 2.42 24200 36.4 60 1.42 34 <2 6.29 62900 13 406 1.7 <5 1.92 19200 <1 13 55 38.5 3.83 38300 2.06 20600 38.4 57 1.14 35 <2 7 70000 12 434 1.9 <5 2.6 26000 <1 14 55 41.4 4.22 42200 2.48 24800 34.5 60 1.41 36 <2 6.23 62300 10 415 1.7 <5 2.4 24000 <1 13 46 37.3 3.72 37200 2.17 21700 33.7 56 1.3 37 <2 6.5 65000 10 421 1.9 <5 2.25 22500 <1 15 60 26.2 3.97 39700 2.21 22100 33.7 58 1.3 38 <2 6.58 65800 11 423 1.9 <5 2.35 23500 <1 14 59 28.3 3.98 39800 2.28 22800 32 59 1.33 39 <2 6.5 65000 12 425 1.9 <5 2.1 21000 <1 14 59 32.8 3.99 39900 2.23 22300 33.3 60 1.26 129 40 <2 4.65 46500 10 307 1.3 <5 1.26 12600 <1 9 38 35.1 3.19 31900 1.41 14100 28.7 39 0.77 41 <2 4 40000 9 277 1.1 <5 1.32 13200 <1 9 33 31.1 3.01 30100 1.25 12500 24.2 32 0.75 42 <2 6.75 67500 11 429 1.9 <5 2.48 24800 <1 15 54 28.5 4.1 41000 2.39 23900 32.5 59 1.38 43 <2 6.21 62100 14 395 1.8 <5 2.09 20900 <1 13 55 29.4 3.89 38900 2.11 21100 28.4 54 1.2 44 <2 6.07 60700 11 396 1.6 <5 2.16 21600 <1 12 47 33.4 3.79 37900 2.01 20100 30.8 53 1.19 49 <2 6.99 69900 13 454 1.9 <5 2.46 24600 <1 14 56 57.3 4.1 41000 2.44 24400 33 59 1.42 53 <2 6.04 60400 10 409 1.7 <5 1.9 19000 <1 13 50 54.1 3.7 37000 1.93 19300 35 55 1.12 59 <2 4.46 44600 18 318 1.2 <5 1.39 13900 <1 11 33 33.5 3.85 38500 1.39 13900 31.5 34 0.76 60 <2 5.63 56300 10 369 1.6 <5 2.14 21400 <1 12 47 27.9 3.57 35700 1.91 19100 28.3 48 1.16 61 <2 4.68 46800 12 321 1.3 <5 1.48 14800 <1 10 38 31.5 3.35 33500 1.42 14200 28.7 39 0.87 62 <2 5.95 59500 11 406 1.7 <5 1.94 19400 <1 12 50 33.2 3.77 37700 1.91 19100 32.1 54 1.13 65 <2 6.66 66600 11 450 1.9 <5 0.43 4300 <1 13 57 65.9 4.54 45400 2.23 22300 29.6 51 0.87 67 <2 5.01 50100 11 339 1.4 <5 1.57 15700 <1 10 41 29.4 3.29 32900 1.54 15400 27.7 42 0.94 71 <2 6.72 67200 5 457 1.7 <5 4.34 43400 <1 13 53 43.9 4.05 40500 2.47 24700 28.6 43 1.99 72 <2 5.48 54800 13 364 1.5 <5 1.73 17300 <1 11 44 34.4 3.65 36500 1.74 17400 32.8 48 1.01 Mean b-d 6.22 62227.27 11.09 404.91 1.73 b-d 2.12 21245.45 b-d 13.15 51.94 36.05 3.90 39006.06 2.11 21118.18 33.00 54.33 1.21 n= 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33

30 <2 6.7 67000 9 471 1.9 <5 2.12 21200 <1 15 54 31.1 4.27 42700 2.32 23200 39.4 52 1.22 31 <2 6.3 63000 10 448 1.8 <5 2.35 23500 <1 14 52 39.6 3.78 37800 2.11 21100 38.4 53 1.41 32 <2 6.68 66800 12 478 1.9 <5 1.79 17900 <1 14 55 35.4 4.06 40600 2.16 21600 41.3 54 1.06 33 <2 6.7 67000 11 467 1.9 <5 1.89 18900 <1 14 54 34.2 4.14 41400 2.19 21900 40.1 55 1.13 48 <2 6.62 66200 20 521 2.1 <5 0.53 5300 <1 19 50 56.2 6.21 62100 2 20000 43.9 59 0.6 58 <2 7.19 71900 9 487 1.9 <5 3.3 33000 <1 15 56 42.6 4.22 42200 2.55 25500 34 44 1.52 64 <2 6.21 62100 13 517 1.7 <5 0.61 6100 <1 13 47 49.9 4.33 43300 2.23 22300 41.2 37 0.77 Mean b-d 6.63 66285.71 12.00 484.14 1.89 b-d 1.80 17985.71 b-d 14.86 52.57 41.29 4.43 44300.00 2.22 22228.57 39.76 50.57 1.10 n= 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7

Grimsby shale 80 <2 2.77 27700 <3 152 0.9 <5 12.6 126000 <1 16 18 8.3 3.46 34600 1.71 17100 43.6 25 4.43 Grimsby weath81 <2 7.71 77100 6 414 2.5 <5 3.64 36400 <1 17 52 10.4 7.58 75800 3.54 35400 38.3 70 1.51 Queenston 82 <2 8.04 80400 <3 441 2.2 <5 1.88 18800 <1 19 58 15.8 5.29 52900 3.71 37100 39 63 1.97 Grimsby83 <2 1.44 14400 <3 88 <0.5 <5 0.06 600 <1 145 7 6.1 0.26 2600 0.01 100 16.2 17 <0.01 Black LS 84 <2 0.25 2500 8 60 0.5 <5 >15 4 11 8 37.1 1.42 14200 0.09 900 2.1 2 0.41 APPENDIX F CHEMICAL ANALYSES OF SILT AND CLAY FRACTION AND SOURCE ROCKS (CONTINUED)

Analyte Ag Al Al As Ba Be Bi Ca Ca Cd Co Cr Cu Fe Fe K K La Li Mg Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 0.01 3 1 0.5 5 0.01 1 1 1 0.5 0.01 0.01 0.5 1 0.01 Units PPM % PPM PPM PPM PPM PPM % PPM PPM PPM PPM PPM % PPM % PPM PPM PPM % dkgray LS85 <2 0.77 7700 6 105 0.7 <5 >15 <1 14 13 14.2 0.86 8600 0.25 2500 6.3 3 0.56 gray LS 86 <2 0.22 2200 9 5380 <0.5 <5 >15 <1 6 4 8.2 1.07 10700 0.09 900 1.6 <1 0.47 gray Queenston 87 3 6.65 66500 50 348 1.9 <5 4.42 44200 <1 22 42 2020 2.81 28100 3.18 31800 36.2 58 2

DUP-1 <2 3.93 39300 13 272 1.1 <5 1.73 17300 <1 9 34 48.7 3.49 34900 1.14 11400 29.9 29 0.75 DUP-15 <2 6.69 66900 13 446 1.9 <5 1.67 16700 <1 14 55 126 3.8 38000 2.06 20600 36.6 65 1.14 DUP-69 <2 9.26 92600 5 527 2.2 <5 0.56 5600 <1 12 68 45.9 3.07 30700 2.33 23300 42.6 60 0.72 DUP-20 <2 7.17 71700 10 457 2 <5 2.38 23800 <1 16 58 30.2 4.21 42100 2.39 23900 32.1 62 1.39 DUP-36 <2 6.9 69000 12 422 1.7 <5 2.43 24300 <1 13 50 39.4 4.09 40900 2.28 22800 30.1 56 1.38 DUP-60 <2 6.1 61000 11 400 1.8 <5 2.33 23300 <1 14 53 31.7 3.82 38200 2.02 20200 29.9 49 1.22 DUP-55 L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. 55 L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R.

duplicate 71-76 <2 6.2 0.00062 8 423 1.6 <5 4.25 42500 <1 20 45 28.4 3.68 36800 2.2 22000 28.4 44 1.82 130 APPENDIX F CHEMICAL ANALYSES OF SILT AND CLAY FRACTION AND SOURCE ROCKS (CONTINUED)

Analyte Mg Mn Mo Na Na Ni P P Pb Sb Sc Sn Sr Ti Ti V W Y Zn Zr Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 1 0.01 1 0.01 2 5 0.5 10 0.5 0.01 2 10 0.5 0.5 0.5 Units PPM PPM PPM % PPM PPM % PPM PPM PPM PPM PPM PPM % PPM PPM PPM PPM PPM PPM 1 7500 480 1 0.62 6200 21 0.06 600 20 <5 7.1 <10 91.6 0.24 2400 50 <10 20.5 86.8 232 2 8300 676 1 0.61 6100 27 0.07 700 26 6 8.3 <10 90.1 0.26 2600 60 <10 21.1 97.9 212 3 8000 477 1 0.59 5900 26 0.06 600 21 5 8.5 <10 91.4 0.25 2500 61 <10 19.1 81.7 176 4 7800 482 <1 0.63 6300 24 0.06 600 18 <5 8.2 <10 91.2 0.25 2500 59 <10 20 78.6 195 5 7400 451 <1 0.67 6700 21 0.06 600 18 <5 7.1 <10 88 0.25 2500 50 <10 20.8 81.8 216 7 9400 545 1 0.51 5100 32 0.06 600 21 7 11.7 <10 103 0.28 2800 89 <10 18.8 99 143 8 7200 440 <1 0.66 6600 21 0.06 600 18 <5 7 <10 85 0.25 2500 49 <10 21.2 83.6 226 9 7600 464 1 0.67 6700 24 0.06 600 21 <5 7.6 <10 88 0.26 2600 53 <10 22.4 79.2 245 10 7500 448 1 0.66 6600 23 0.06 600 21 <5 7.1 <10 84.9 0.25 2500 49 <10 21.9 89 247 11 7700 436 <1 0.62 6200 25 0.06 600 21 <5 8.1 <10 85.7 0.24 2400 59 <10 19.9 79.3 192 12 8400 483 <1 0.65 6500 25 0.06 600 18 <5 8.2 <10 89.4 0.25 2500 58 <10 20.4 80.8 206 13 10000 496 <1 0.57 5700 35 0.06 600 20 7 11.2 <10 100 0.29 2900 83 <10 19.9 91.3 163 15 11000 474 1 0.55 5500 35 0.06 600 26 8 12.5 10 98.8 0.24 2400 100 <10 18.9 94.8 134 16 12400 465 1 0.6 6000 41 0.06 600 20 8 12.5 <10 111 0.28 2800 103 <10 18.1 88.5 131 45 12000 471 1 0.63 6300 31 0.06 600 17 6 11.2 <10 110 0.25 2500 87 <10 18.5 79.9 141 46 12700 482 2 0.59 5900 34 0.06 600 17 7 12.3 <10 113 0.27 2700 99 <10 18.5 79.8 132 131 47 8400 434 <1 0.51 5100 29 0.06 600 22 6 10.5 <10 90 0.26 2600 79 <10 18.6 82.2 157 50 16500 663 <1 0.74 7400 34 0.07 700 15 5 12.7 <10 147 0.32 3200 105 <10 20.8 80.1 118 51 8200 495 1 0.51 5100 27 0.06 600 23 7 9.7 <10 89 0.26 2600 73 <10 18.5 85.8 161 52 10800 523 1 0.61 6100 30 0.06 600 18 7 11.1 <10 102 0.27 2700 85 <10 19.6 83.9 155 54 8800 494 <1 0.64 6400 22 0.06 600 26 6 8.4 <10 94.8 0.25 2500 62 <10 19.6 85.9 187 57 11100 498 <1 0.63 6300 32 0.06 600 19 6 11 <10 103 0.27 2700 86 <10 18.3 78.5 143 63 12100 581 <1 0.54 5400 33 0.06 600 18 6 12.6 <10 112 0.28 2800 97 <10 20 86.2 144 68 13100 540 1 0.63 6300 29 0.07 700 19 6 11 <10 125 0.29 2900 73 <10 20.7 79.9 160 69 6900 312 2 0.27 2700 30 0.04 400 21 7 15.3 <10 113 0.35 3500 110 <10 18.5 87 146 70 8800 361 1 0.46 4600 30 0.06 600 19 7 12.6 <10 98.7 0.29 2900 92 <10 19.7 93.5 154 77 6500 828 <1 0.59 5900 25 0.07 700 25 7 7.9 <10 129 0.18 1800 55 220 17.5 97.7 87.6 78 11100 510 1 0.48 4800 18 0.05 500 16 <5 6.2 <10 96.2 0.17 1700 40 370 14.2 88.5 95.9 Mean 9542.86 500.32 1.13 0.59 5871.43 28.00 0.06 603.57 20.14 6.53 9.91 10.00 100.74 0.26 2607.14 73.79 295.00 19.50 85.76 167.84 n= 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28

6 6200 623 1 0.59 5900 25 0.06 600 24 6 8.9 <10 85.1 0.25 2500 66 <10 20.4 98 183 17 13500 1390 <1 0.48 4800 36 0.07 700 40 7 10.5 <10 96.9 0.22 2200 69 <10 21 143 153 18 18400 5840 2 0.38 3800 64 0.06 600 98 10 10.6 <10 83.8 0.19 1900 69 <10 23 234 142 56 9800 480 <1 0.57 5700 29 0.06 600 19 5 11.2 <10 99.9 0.26 2600 86 <10 19.5 85.3 146 66 5300 485 <1 0.57 5700 24 0.07 700 20 8 10.2 <10 83.6 0.25 2500 72 <10 22 104 174 Mean 10640.00 1763.60 1.50 0.52 5180.00 35.60 0.06 640.00 40.20 7.20 10.28 b-d 89.86 0.23 2340.00 72.40 b-d 21.18 132.86 159.60 n= 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

14 13500 568 2 0.62 6200 34 0.06 600 16 6 12.3 <10 119 0.28 2800 98 <10 19.7 80.4 128 19 14200 564 2 0.61 6100 35 0.07 700 17 7 13 <10 119 0.29 2900 91 <10 20.4 80.1 128 20 13900 549 1 0.6 6000 35 0.06 600 18 8 13.5 <10 113 0.24 2400 108 <10 20.7 86.7 121 21 13000 524 2 0.59 5900 34 0.07 700 20 5 12.9 <10 115 0.29 2900 102 <10 20.4 83.7 143 22 11500 493 1 0.55 5500 32 0.06 600 18 8 11.9 <10 103 0.29 2900 93 <10 19.8 82.6 150 23 11700 504 1 0.6 6000 31 0.06 600 18 7 11.5 <10 104 0.28 2800 90 <10 20 83.7 150 24 11500 504 1 0.59 5900 31 0.06 600 19 8 12 <10 104 0.29 2900 93 <10 20.2 82.6 158 25 12500 517 1 0.62 6200 32 0.06 600 24 7 12 <10 110 0.28 2800 95 <10 20 80.9 148 26 12600 528 2 0.58 5800 34 0.06 600 19 7 12.3 <10 109 0.31 3100 98 <10 20.8 87.1 155 27 13600 563 2 0.6 6000 33 0.07 700 16 7 12.7 <10 117 0.29 2900 101 <10 20.3 79.1 130 APPENDIX F CHEMICAL ANALYSES OF SILT AND CLAY FRACTION AND SOURCE ROCKS (CONTINUED)

Analyte Mg Mn Mo Na Na Ni P P Pb Sb Sc Sn Sr Ti Ti V W Y Zn Zr Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 1 0.01 1 0.01 2 5 0.5 10 0.5 0.01 2 10 0.5 0.5 0.5 Units PPM PPM PPM % PPM PPM % PPM PPM PPM PPM PPM PPM % PPM PPM PPM PPM PPM PPM 28 14300 559 1 0.61 6100 33 0.07 700 20 6 12.3 <10 120 0.28 2800 98 <10 20.5 83.7 137 29 14200 553 1 0.62 6200 34 0.07 700 18 8 12.3 <10 121 0.31 3100 97 <10 20.9 83.5 141 34 11400 477 1 0.58 5800 33 0.06 600 20 6 11.3 <10 102 0.29 2900 88 <10 20 80.8 154 35 14100 529 2 0.63 6300 34 0.06 600 17 6 12.6 <10 120 0.31 3100 101 <10 20.4 80.3 132 36 13000 491 1 0.62 6200 29 0.06 600 16 8 11.4 <10 112 0.21 2100 91 <10 18.8 72.8 119 37 13000 524 2 0.57 5700 32 0.06 600 18 8 12 <10 109 0.29 2900 91 <10 19.8 80.6 139 38 13300 535 2 0.6 6000 32 0.06 600 17 6 12.2 <10 111 0.29 2900 98 <10 19.7 82.3 131 39 12600 525 1 0.59 5900 32 0.06 600 16 7 12.2 <10 105 0.29 2900 97 <10 19.9 80.9 143 40 7700 466 <1 0.6 6000 21 0.06 600 20 <5 7.9 <10 77.1 0.19 1900 57 <10 17.7 83.1 156 41 7500 442 <1 0.61 6100 19 0.06 600 16 5 7 <10 75.4 0.19 1900 49 <10 18.3 73.1 177 42 13800 538 2 0.63 6300 33 0.06 600 18 9 12.4 <10 110 0.23 2300 99 <10 19 78.7 117 43 12000 468 1 0.63 6300 30 0.05 500 17 7 11.1 <10 99.5 0.21 2100 91 <10 17.2 75.3 117 44 11900 484 1 0.59 5900 29 0.06 600 18 7 10.5 <10 103 0.21 2100 80 <10 17.3 74.4 112 49 14200 561 <1 0.61 6100 34 0.06 600 19 7 12.8 <10 114 0.23 2300 108 <10 18.4 85.2 113 53 11200 552 1 0.58 5800 29 0.06 600 21 7 10.8 <10 98.7 0.23 2300 84 <10 18.8 87.5 135 59 7600 349 <1 0.63 6300 21 0.07 700 16 6 7.6 <10 81.4 0.18 1800 54 <10 18.8 84.8 147 132 60 11600 482 1 0.59 5900 28 0.06 600 16 6 10.3 <10 95.4 0.21 2100 80 <10 18.3 72.3 127 61 8700 467 <1 0.57 5700 22 0.06 600 18 6 8.3 <10 81.1 0.19 1900 59 <10 18.7 72.5 161 62 11300 521 <1 0.57 5700 28 0.06 600 18 7 10.5 <10 99.1 0.23 2300 80 <10 19 79.2 143 65 8700 517 1 0.64 6400 32 0.08 800 23 9 12.2 <10 90.5 0.25 2500 95 <10 22.3 97.2 148 67 9400 436 <1 0.58 5800 24 0.06 600 18 6 8.6 <10 87.8 0.21 2100 63 <10 17.8 74.4 142 71 19900 673 <1 0.88 8800 29 0.08 800 16 6 11.4 <10 164 0.27 2700 95 <10 21.4 72.1 107 72 10100 472 1 0.58 5800 26 0.06 600 18 7 9.6 <10 91.3 0.2 2000 72 <10 17.9 80.2 137 Mean 12106.06 513.18 1.36 0.61 6081.82 30.15 0.06 627.27 18.15 6.88 11.25 b-d 105.49 0.25 2527.27 87.76 b-d 19.49 80.66 137.76 n= 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33

30 12200 626 <1 0.59 5900 34 0.07 700 20 8 12.4 <10 111 0.23 2300 98 <10 20 90.9 121 31 14100 455 <1 0.56 5600 33 0.06 600 21 7 11.8 <10 102 0.2 2000 94 <10 19.6 129 124 32 10600 444 <1 0.58 5800 32 0.06 600 20 7 12 <10 103 0.23 2300 93 <10 20.3 96.5 131 33 11300 397 <1 0.54 5400 34 0.06 600 20 7 12.3 <10 99.8 0.25 2500 97 <10 19.5 108 125 48 6000 1870 2 0.45 4500 46 0.13 1300 40 8 12.5 <10 85.8 0.22 2200 91 <10 24.4 158 131 58 15200 713 <1 0.74 7400 33 0.08 800 17 7 12.8 <10 144 0.3 3000 107 <10 21.7 80.7 115 64 7700 815 1 0.77 7700 27 0.1 1000 23 7 11 <10 112 0.26 2600 86 <10 24.1 102 161 Mean 11014.29 760.00 1.50 0.60 6042.86 34.14 0.08 800.00 23.00 7.29 12.11 b-d 108.23 0.24 2414.29 95.14 b-d 21.37 109.30 129.71 n= 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7

Grimsby shale 80 44300 1860 <1 0.06 600 12 0.28 2800 4 <5 13.5 <10 105 0.14 1400 49 80 59.3 54.2 92.1 Grimsby weath81 15100 700 <1 0.12 1200 32 0.15 1500 12 10 14.5 <10 86.2 0.29 2900 124 20 31.1 107 136 Queenston 82 19700 582 1 0.09 900 38 0.07 700 12 9 14.7 <10 92 0.3 3000 126 10 21.3 82.4 104 Grimsby83 17 1 <0.01 1 0.03 300 4 <5 2 <10 224 0.03 300 3 420 5.8 4.9 51 Black LS 84 4100 1030 <1 0.02 200 9 0.11 1100 11 <5 <0.5 <10 481 0.01 100 9 60 2.6 246 4.1 dkgray LS85 5600 788 1 0.03 300 25 0.08 800 17 <5 1.4 <10 757 0.02 200 14 30 6.1 27.1 9.7 gray LS 86 4700 479 <1 0.02 200 5 0.01 100 <2 <5 <0.5 <10 689 <0.01 3 20 1.6 7.1 3.7 gray Queenston 87 20000 817 2 0.14 1400 42 0.08 800 10 5 12.7 <10 79.5 0.24 2400 118 30 30.3 72.1 145

DUP-1 7500 474 1 0.58 5800 21 0.06 600 22 <5 7.1 <10 84.3 0.23 2300 51 <10 21.2 84.5 234 DUP-15 11400 477 1 0.49 4900 33 0.06 600 27 7 12.5 <10 95.4 0.23 2300 102 <10 18 91.2 124 DUP-69 7200 316 1 0.27 2700 30 0.04 400 20 6 15 <10 108 0.32 3200 111 <10 17.5 89.1 136 APPENDIX F CHEMICAL ANALYSES OF SILT AND CLAY FRACTION AND SOURCE ROCKS (CONTINUED)

Analyte Mg Mn Mo Na Na Ni P P Pb Sb Sc Sn Sr Ti Ti V W Y Zn Zr Method ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B ICP40B Detection 2 1 0.01 1 0.01 2 5 0.5 10 0.5 0.01 2 10 0.5 0.5 0.5 Units PPM PPM PPM % PPM PPM % PPM PPM PPM PPM PPM PPM % PPM PPM PPM PPM PPM PPM DUP-20 13900 533 1 0.53 5300 35 0.06 600 19 9 13.1 <10 106 0.23 2300 107 <10 18.6 84.2 117 DUP-36 13800 505 1 0.65 6500 30 0.06 600 17 6 11.1 <10 116 0.22 2200 91 <10 17.4 76.4 111 DUP-60 12200 493 1 0.61 6100 30 0.07 700 17 5 10.9 <10 101 0.23 2300 87 <10 19.7 74.8 141 DUP-55 L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. 55 L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R. L.N.R.

duplicate 71-76 18200 663 1 0.73 7300 29 0.07 700 14 6 10.4 <10 140 0.24 2400 84 90 18.8 67.4 99.6

133