A Geochemical Study of Four Prehistoric Quarries in Oaxaca, Mexico

Home , Economy of Oaxaca, Ronald Spores, Sierra Madre del Sur, Tlaxiaco

A GEOCHEMICAL STUDY OF FOUR PREHISTORIC QUARRIES IN OAXACA, MEXICO.

MICHELLE L. TROGDON

(Under the direction of Ervan Garrison)

ABSTRACT

Petrographic and geochemical analyses of chert quarries used in antiquity for stone tool production in the Mixteca Alta, Oaxaca, Mexico have shown some promising results. This study combines petrography, electron microprobe analysis, hydrofluoric acid treatment, and isotope analysis to identify differences between four quarries and build a database of characteristics associated with each quarry. Major elements in trace amounts (Al, Ca, Na, Mg, and K) and their distribution, fossils, and δ18O values were unable to distinguish unique characteristics of the four quarries presented. However, these methods did reveal interesting information regarding chert formation in general and specific processes that influenced chert formation in Oaxaca.

INDEX WORDS: Archaeological Geology, Oaxaca, Mixteca Alta, Chert, Electron Microprobe Analysis, Stable Isotopes.

A GEOCHEMICAL STUDY OF FOUR PREHISTORIC QUARRIES IN OAXACA, MEXICO.

MICHELLE L. TROGDON

B.S., Allegheny College, 2004

A Thesis Submitted to the Graduate Faculty of The University of Georgia in Partial Fulfillment

of the Requirements for the Degree

MASTER OF SCIENCE

ATHENS, GEORGIA

2007

MICHELLE L. TROGDON

A GEOCHEMICAL STUDY OF FOUR PREHISTORIC QUARRIES IN OAXACA, MEXICO.

MICHELLE L. TROGDON

Major Professor: Ervan Garrison

Committee: Samuel E. Swanson Stephen A. Kowalewski

Electronic Version Approved:

Maureen Grasso Dean of the Graduate School The University of Georgia December 2007

DEDICATION

To my mother.

ACKNOWLEDGEMENTS

Thank you to my wonderful committee at the University of Georgia; UGA, Watts-

Wheeler, CLACS, SAAS; special thanks to INAH; Dr. Ronald Spores and Dr. Nelly Robles co-

directors of the Pueblo Viejo project; the community of Teposcolula; the ancient Mixtec people;

Mis chicas arqueologicas de Pueblo Viejo; mi guia don Benito; Sheldon Skaggs; Chris Fleisher;

Julie Cox; Viorel Atudorei; Doug Crowe; Bruce Railsback; Meg Kinsella; my family for never understanding exactly what I do, but always intently listening; my friends and those whom have

gone before me for also listening and helping me find motivation; and lastly my dog for never ever eating my thesis (just my students’ homework).

TABLE OF CONTENTS

Page

ACKNOWLEDGEMENTS...... v

LIST OF TABLES...... viii

LIST OF FIGURES ...... ix

CHAPTER

1 INTRODUCTION ...... 1

2 ARCHAEOLOGICAL PROBLEM...... 7

Lithics in Oaxaca...... 7

Postclassic Period...... 12

El Fortin (TE 2) ...... 13

Tixa Viejo (TE 127) ...... 14

Pueblo Viejo (TE 1) ...... 15

Conclusions ...... 17

3 GEOLOGICAL SETTING...... 19

Tectonic Setting...... 19

Geology of the study area...... 21

Quarry Stratigraphy...... 26

4 CLASSIFICATION AND PROPERTIES OF CHERT...... 32

Formation processes and varieties of chert ...... 32

Physical properties ...... 34

Chemical properties...... 36

5 METHODS ...... 38

X-Ray Diffraction...... 38

Petrography ...... 39

Hydrofluoric Acid Treatment...... 39

Electron Microprobe Analysis...... 39

Stable Isotope ...... 40

6 RESULTS ...... 43

Physical properties and Petrography ...... 43

Hydrofluoric Acid Treatment...... 46

Electron Microprobe Analysis...... 49

Stable Isotope ...... 57

7 DISCUSSION & CONCLUSIONS...... 61

Physical properties and Petrography ...... 61

Hydrofluoric Acid Treatment...... 63

Electron Microprobe Analysis...... 63

Stable Isotope ...... 64

Conclusions ...... 65

REFERENCES ...... 67

APPENDICES ...... 81

A All chert samples and the various methods used in this study...... 81

B Peak positions in degrees and d-spacing and relative intensity of XRD samples ...... 84

C EMP results for all four quarries. Thirty points were measured per sample ...... 87

D Stable isotope values of chert and host carbonate rock for all four quarries ...... 118

vii

LIST OF TABLES

Page

Table 2.1: The phases of the Mixteca Alta through time (modified from Balkansky et al., 2000) .8

Table 2.2: Gray and green obsidian distribution at three sites in the Teposcolula Valley ...... 14

Table 6.1: Thin section observations from four quarries...... 44

Table 6.2: Daily Electron Microprobe Analysis minimum detection limits...... 50

Table 6.3: Daily EMP measurements of a quartz standard...... 50

Table 6.4: Average of points above EMP minimum detection limits for nine samples from the

quarry of Yolomecatl...... 51

Table 6.5: Average of points above EMPA minimum detection limits for nine samples from the

quarry of Chilapa...... 53

Table 6.6: Average of points above EMPA minimum detection limits for nine samples from the

quarry of San Felipe Ixtapa ...... 55

Table 6.7: Average of points above EMPA minimum detection limits for nine samples from the

quarry of Prieto...... 56

Table 6.8: Isotopic composition (‰) of chert samples from all quarries ...... 58

viii

LIST OF FIGURES

Page

Figure 1.1 Geologic map of the study area in Oaxaca, Mexico. The green unit represents the

Cretaceous deposits including eight formations. Pueblo Viejo is the archaeological site

of interest and Yolomecatl, Chilapa, San Felipe Ixtapa, and Prieto are the proposed

quarries ...... 4

Figure 2.1 The Mixteca Alta is located in the west-central portion of the state of Oaxaca...... 8

Figure 2.2 The quarry of Prieto shown here appears to be a large pile of debris in fact was a site

for initial core testing (1m scale)...... 9

Figure 2.3 Postclassic settlement in the Teposcolula Valley. Three sites of interest in this study

include El Fortin, Tixa Viejo, and Pueblo Viejo. Black indicates settlement (from

Stiver, 2001) ...... 11

Figure 3.1 (A) Location of the study area. (B) The Sierra Madre del Sur is delineated by the

dotted line and continues south to the coast. Tectonostratigraphic terranes comprising

southern Mexico include: Ju- Juarez terrane (Cuicateco), Gr- Guerrero terrane, Ma-

Maya terrane, Mt- Mixteca terrane, Ox- Oaxaca terrane (Zapotec), Xo- Xolapa terrane.

paleogeographic units and major structures obtained from maps and texts used in this

work. The location of the field areas referenced in this study follow: 1. Hernandez-

Romano, (1997), 2. Garza, (2003), 3. Böhnel, (1999), 4. Ferrusquia, (1971), 5. Alaniz-

Alvarez et.al., (1994), 6. field area for this study (refer to Figure 3.4), 7. Urrutia and

Ferrusquia, (2001) (modified from Nieto-Samaniego et. al., 2006)...... 20

Figure 3.2 Chevron folds in the Zapotitlan Fm...... 22

Figure 3.3 Milliolid in the Teposcolula Fm. Bar = 250µm...... 23

Figure 3.4 The stratigraphy in the Teposcolula Valley consists of several chert bearing Tertiary

and Cretaceous units overlying earlier Mesozoic deposits and the Oaxacan Complex.

Multiple representations of the stratigraphy of the valley from NW to SE from the

following: A. Böhnel, (1999), B. Böhnel, (1999), C. Nieto-Samaniego and others,

(2006), D. Urrutia and Ferrusquia, (2001), E. this study. (see also Figure 3.1)...... 25

Figure 3.5 The study area is divided by the contact between two terranes, the Mixteco to the west

and the Zapoteco to the east (modified from INEGI, 1984) ...... 27

Figure 3.6 The hillside outcrop at Yolomecatl exposes the Teposcolula Fm. and chert-rich layers

(1 meter scale) ...... 28

Figure 3.7 A fresh road cut exposes 3m of the Chilapa Fm. near the modern town of Chilapa del

Diaz ...... 29

Figure 3.8 The hillside exposure of Cretaceous limestone and chert-rich layers at San Felipe

Ixtapa...... 29

Figure 3.9 Chert-rich layers in the Teposcolula limestone were several centimeters thick at San

Felipe Ixtapa...... 30

Figure 3.10 A possible testing area for flint knappers in antiquity littered with chert debitage at

San Felipe Ixtapa (1 meter scale) ...... 30

Figure 3.11 A preliminary testing site for chert cobbles extracted from the Chilapa Fm. at Prieto

(1 meter scale) ...... 31

Figure 4.1 This schematic represents permeable carbonate deposits at near shore mixing zones

and interaction with meteoric water contributing to the formation of chert (from

Knauth, 1994)...... 33

Figure 4.2 A general diagram of the pathways in which chert can form and the factors limiting

formation (from Knauth, 1994)...... 35

Figure 4.3 Framework silicates consist of one Si+4 and four O-2 in a three-dimensional

tetrahedron...... 37

Figure 6.1 Microquartz growth isolated insoluble material to thin bands between quartz crystals.

Bar = 500µm...... 45

Figure 6.2 Microquartz and chalcedony are replacing carbonate grains. Bar = 500µm...... 45

Figure 6.3 The interface between the chert (left) and the carbonate host rock is not clearly

defined as microquartz replaced carbonate grains. Bar = 250µm ...... 46

Figure 6.4 This well preserved bivalve was one of very few in hydrofluoric acid etched YOLO

samples. Bar = 1/16mm...... 47

Figure 6.5 Minor amounts of hematite were observed in SFI hydrofluoric acid etched samples.

Bar = 1/16mm...... 48

Figure 6.6 Abundant bivalves etched with HF acid in sample PRI-CH-1 were characteristic of

that quarry. Bar = 1/8mm ...... 49

Figure 6.7 Aluminum and magnesium oxide content from two samples representing the quarry of

Yolomecatl ...... 51

Figure 6.8 Points from each quarry with measurable amounts of Al2O3, MgO, and CaO above

minimum detection. Samples from SFI did not have measurable amounts of each

element in any point analyzed...... 52

Figure 6.9 Figure 6.10 Aluminum and magnesium oxide content from only one sample

representing the quarry of Chilapa ...... 54

Figure 6.10 Figure 6.11 Aluminum and magnesium oxide content from seven samples

representing the quarry of Prieto ...... 57

Figure 6.11 δ18O values of silicates and carbonate host rocks of all quarries ...... 59

xii

CHAPTER ONE

INTRODUCTION

This study investigates chemical and compositional differences in chert resources or quarries found in the northwest region of Oaxaca, México and the implications on stone tool production and exchange in the ancient Oaxacan economy. Quarry is defined as “a source of raw material where stoneworking (knapping) is usually limited to testing material quality and preliminary shaping” in order to determine the suitability of the material for further stone tool production (Moholy-Nagy, 1990: 269). Chert is one of the only locally occurring economic resource that there is archaeological evidence for at prehistoric archaeological sites in Oaxaca yet little research has focused on the production and trade of these resources (Fargher, 2004: 32; Feimann et. al., 2002: 252). I hypothesize significant compositional differences exist between the chert sources examined in this study. These differences contribute to the overall quality of the chert thereby making it more or less desirable for Mixteca stone tool production. This study employs geochemical and archaeometric techniques including treatment with hydrofluoric acid, petrography, electron microprobe analysis, and stable isotope analysis in order to differentiate between local sources and identify characteristics contributing to the overall quality and desirability of chert.

Since the 1960s the application of chemical analytical techniques has been widely employed in American archaeology (Akridge et. at., 2001; Cameron, 2001; Fargher,

2004: 29; Glascock and Neff, 2003; Hatch and Miller, 1985; Healy et. al., 1984; Hoard et al., 1993; Luedtke, 1978, 1979; Melcher et. al., 1977; Piecouet, 1999; Reimold et. al.,

2003). In Mesoamerica specifically, such techniques in support of craft specialization and

1 provenance research have increased exponentially in the field of archaeology (Sheets,

1977; 140). Research questions addressing the origin of stone and metal artifacts in

particular have benefited significantly from the use of geochemical analytical techniques.

Identifying the origin or provenance of an artifact has significant insight into cultural

questions. Before the onset of metallurgy, lithic or stone and bone tools were common artifacts in prehistory. In Mesoamerica, metallurgy was generally reserved for symbolic use and stone tools were crafted for utilitarian purposes. This stone industry produced beautifully crafted objects and was, therefore, dependent on good quality lithic resources.

Obsidian was often the material of choice for lithic tools and widely traded across

Mesoamerica (Whalen, 1983: 24). While obsidian may have been abundant, it was not ubiquitous causing ancient peoples to substitute it with a lesser quality, but more locally available material such as chert or flint. Stone tools are readily found well preserved in archaeological assemblages. With the exception of heat treating, the production process did not change the integrity of the original chert used to make a stone tool.

Historically, local chert resources have been widely exploited. Aoyama (1994) for example found chipped stone to be correlated with socioeconomics in prehistoric

Honduras. A better understanding of this resource’s geography, geology, and production will provide insight into the ancient economy of Oaxaca. Obsidian and chert tools in the archaeological record are related to long distance trade, access to exotic materials, and increasing societal complexities such as class systems in ancient Mexico. Chert resources have been used throughout Mesoamerican history including present day. For example, pieces of chert are combined, cut, and polished for floor tiles at the town hall in the municipal of Yolomecatl today. The specific quarries or chert mines chosen for this study

2 have been demonstrated to have produced chert for tools in antiquity. The detailed geological study of these quarries has not been undertaken until now. Chert quarries have been identified in the modern cities of Chilapa del Diaz, Yolomecatl, San Felipe Ixtapa,

Teposcolula, and Nochixtlan which is located approximately 55 km northwest of Oaxaca

City, Mexico (Figure 1.1). These five modern cities are within 10 km of Pueblo Viejo, an archaeological site inhabited by the Mixtec in the Classic and Postclassic periods (200-

1520 AD).

Aesthetically, chert varies in color, luster, and quality from quarry to quarry, but remaines reasonably consistent within each quarry. Arbitrarily selected surface collection artifacts (n= 100) and excavated artifacts (n= 100) appear to have similar visual characteristics to hand samples from quarries. Because of dissimilar diagenesis related to geographic differences as well as the juxtaposition of chert within the carbonate deposits, distinguishing geochemical properties should exist. The most widely used archaeometric technique for chert provenance research has been Neutron Activation Analysis (NAA) and, more commonly today, Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

Previous studies have employed Neutron Activation Analysis (NAA) with limited success to address trace element composition and the provenance of stone tools

(Glascock and Neff, 2003). NAA has been used with some success to differentiate chert outcrops in the Great Plains (Hoard et. al., 1992; Hoard et. al., 1993) and Alaska (Malyk-

Selivanova et. al., 1998). In Belize, samples from chert outcrops analyzed with NAA did not produce distinctions (Cackler et. al., 1999; Hester et al., 1984). Previous studies have been successful using electron microprobe (EMPA) in elemental analysis of geological and archaeological materials (Henderson, 2000; Reed 1996). Reimold and others (2003)

te of interest and Yolomecatl, Yolomecatl, and te of interest fied from INEGI, 1984). proposed quarries (modi eblo Viejo is the archaeological si area in Oaxaca, Mexico. The green unit represents the Cretaceous area in Oaxaca, Mexico. Figure 1.1 Geologic map of the study of the study Figure 1.1 Geologic map deposits including eight formations. Pu Chilapa, San Felipe Ixtapa, and Prieto are the

used EMPA to investigate trace elements in concretionary pyrite grains. EMPA has been

even more successful in characterizing metallurgical slag. Chert nucleation is controlled

by precursor sediment (Gao and Land, 1991). Perhaps investigating major elements in

trace amounts included during precipitation of silica forming chert using EMPA would be characteristic of one deposit and indicative of quality and aesthetic characteristics.

Previous researchers have used stable isotope analyses of oxygen and hydrogen to examine the conditions during chert formation (Behl and Smith, 1990; Gao and Land,

1991; Knauth, 1992; Knauth, 1994; Knauth and Epstein, 1976; Matheney and Knauth,

1993; Sharp, 1990; Sharp et al., 2001; Sharp et. al., 2002). Chert forms shortly after deposition of carbonate sediments therefore stable isotope analyses of chert can be used

to address temperature and composition of interstitial water during the formation process

(Sharp et. al., 2002). In theory, one deposit of chert should have the same isotopic

composition. Isotopic variability would then reflect stratigraphic variation or geographic

extent of a deposit.

Geologically, chert is poorly understood. The homogeneity of most cherts has

compromised the applicability of provenance research. Considering the different factors

which influence the formation of chert obvious differences should exist. Because chert is

approximately 96–99.99% silica (SiO2), chemical differences will be on a small scale.

Visual discrimination has been a long time practice of lithic source identification for archaeologists (Luedtke, 1992). Unfortunately visual characteristics can vary extensively

within one deposit. There are exceptions. Two such instances are (Alibates (TX) and

Gran Pressigny (FR)) where chert is visually distinct multicolored at Alibates (Shaeffer,

5 1958) and ‘honey-brown’ at Gran Pressigny (E. G. Garrison, Personal communication

2006).

Applying new techniques may provide added insight into formation mechanisms of ancient cherts. Since the late 20th century, more instrumental tools have been used to study cherts, notably X-ray diffraction (XRD) (Pretola, 2001), X-ray fluorescence (XRF)

(Shackley, 1998) and inductively coupled plasma-mass spectrometry (ICP-MS) to name the best known of these (Garrison, 2003). Multi-proxy chemical investigation including analysis of hydrogen and oxygen isotopes and trace element analysis using electron microprobe coupled with petrography will confirm quarry variation. Stone tool provenance can then be traced more confidently to specific quarries.

CHAPTER TWO

ARCHAEOLOGICAL PROBLEM

Data regarding lithic assemblages is derived from the Teposcolula Valley Survey

Project (Stiver, 2001). Sites in the Teposcolula Valley are well dated based on ceramic chronology. There are no diagnostic characteristics of lithic tools that provide a chronological sequence. All lithic assemblages are dated by association with ceramics and/or structures. Lithic assemblages like all artifacts are subject to post-depositional formation processes. The original intent of the Teposcolula Valley Survey Project did not include a detailed study of lithic material consequently the characterization of tool types is limited.

Lithics in Oaxaca

The Mixteca Alta is the central portion of the state of Oaxaca in southern Mexico

(Figure 2.1). The relatively high elevation and rugged terrain provided basic necessities for the Mixtecs, who built homes, temples, agricultural terraces, and made stone tools and pottery. The Valley of Teposcolula and adjacent valleys were extremely valuable economically and continue to be fertile and productive for local communities. Attention is focused on lithic production during the Natividad Phase (A.D. 900/950 – 1520/1535)

(Table 2.1). Many of the artifacts excavated are lithics including manos and metates, blades, scrapers, and projectile points crafted from basalt, obsidian, and chert. While obsidian resources utilized are not local and artifacts of this sort are indicative of commerce in the Teposcolula Valley, chert resources were widespread and signify local levels of handicraft production.

Figure 2.1 The Mixteca Alta is located in the west-central portion of the state of Oaxaca.

Table 2.1. The phases of the Mixteca Alta through time (from Balkansky et al., 2000).

Natural resources of chert are found all throughout the valley. Chert production sites in the valley can cover10’s of kilometers in area (Kowalewski, 2004). At Tixa Viejo

8 a site with occupation beginning in the Classic period and continuing into the Postclassic,

residents extracted chert from outcrops within the site (Stiver, 2001:208). Reduction

debris, unfinished bifaces, and debitage reflect specialized knapping at Tixa Viejo,

Colonia Rosario, and El Fortin (Stiver, 2001:209). Fine flakes, bifaces, and points were crafted from preferred clear or whitish chert at these sites.

Elsewhere in the Mixteca Alta local sources were exploited for raw material

(Spores 1969:560). Archaeologists associate finely worked scrapers with workshops that utilized chert from a ridge top in the Nochixtlan Valley commonly known as

Yucunudahui (Stiver, 2001:209). A similar deposit of chert cobbles demonstrating preliminary shaping is located adjacent to Yucunudahui (Figure 2.2). Identified in this study, this is the quarry of Prieto. The summit of these two ridges consists of the remnants of Tertiary limestone containing good quality chert nodules.

Figure 2.2 The quarry of Prieto shown here appears to be a large pile of debris in fact was a site for initial core testing (1m scale).

Much debate in the Mixteca centers on the development of sociopolitical

complexity (Balkansky, 1998; Blanton et. al., 1996; Flannery and Marcus, 1983; Pires

9 and Flannery, 1976; Plunket, 1983). Lithic technology and the use of specific raw sources have been used in support of these arguments regarding sociopolitical change in the

Teposcolula Valley. Handicraft production was especially important in the Teposcolula

Valley to exchange for other goods. I will focus on lithic assemblages from three sites; El

Fortin, Tixa Viejo, and Pueblo Viejo (Figure 2.3).

Large-scale production of lithic tools has been documented in the Valley of

Oaxaca, Hidalgo, and the Basin of Mexico to name a few (Feinman et al., 2002; Healan et al., 1983; Spence, 1981). At Teotihuacán during the Classic Period green obsidian was imported from local raw sources to workshops by the state. Over 1,000 obsidian artifacts were collected and the majority of the raw material used for core-blade technology was green obsidian (Spence, 1981). State domination of this workshop is apparent in its proximity to public structures, standardization of core-blade technology, and the intentional use of green obsidian (Spence, 1981).

Also during the Classic Period at El Palmillo in the Valley of Oaxaca craft

specialization was present at the household level. Local chert resources comprise 93

percent of the chipped stone tools found at El Palmillo (Feinman et al., 2002). Over

20,000 pieces of chert have been documented from excavation. The site is highly

organized on terraces. Lithic reduction is also differentiated between terraces. At terraced

sites in arid climates supplemental handicraft production for economic needs has been

hypothesized (Feinman and Nicholas, 2000; Kowalewski et al., 1989). There is minimal

evidence for status differentiation at El Palmillo and craft production was at the

household level (Feinman, 2002).

Figure 2.3 Postclassic settlement in the Teposcolula Valley. Three sites of interest in this study include El Fortin, Tixa Viejo, and Pueblo Viejo. Black indicates settlement (from Stiver, 2001).

11 Postclassic Period

Following the collapse of Teotihuacán and Monte Alban during the Late Classic period, Mesoamerica during the Postclassic is often described as a period of small competing remnants from previously striving states (Blanton, 1978; Blanton et. al., 1996;

Byland et. al., 1994; Pasztory, 1992). Small factions utilized previous structures and also built new structures and plazas in the Postclassic. Settlement dispersed into valleys sparely inhabited during the Classic period. Many small polities also collapsed without the support and resources provided by alliances with major cities (Balkansky, 1998).

Other small villages demonstrated alliances with Teotihuacán and Monte Alban, but were self-sufficient enough to maintain population during the Postclassic (Joyce, 2001).

After the decline of Teotihuacán, many polities once tied to Teotihuacán began to grapple for prestige and commoner support (Blanton et. al., 1996). Many of these polities were already established during the Classic period with existing structures re-used during the Postclassic. It is possible these polities were under direct control of Teotihuacán, but became unmanageable for elites on the Avenue of the Dead whom were faced with internal and external political tension. Tula in the state of Hidalgo for example, located approximately 70km northwest of Mexico City, was established at the end of the Classic period. Obsidian workshops have been identified at Tula (Healan et. al., 1983). The ceramic assemblage demonstrates the inhabitants’ initial alliance with the Basin of

Mexico and a shift of interests with the ceramic technology representing Tula artisans. It is likely obsidian workshops at Tula were established through Teotihuacán’s expansion of control over obsidian resources, then Tula elites developed the polity independently during Teotihuacán’s collapse (Healan et.al., 1983).

12 Many independent polities competed in the Valley of Oaxaca during the

Postclassic after the collapse of Monte Alban (Kowalewski et. al., 1989; Pohl, 2003).

Status and power were expressed in exotic goods and burial practices (Pohl et. al., 1997).

Ancient people continued to bring offering to plazas at Monte Alban, but this might represent a shared interest in the original meaning applied to the plazas (Pohl et. al.,

1997).

In the Postclassic settlements in the Teposcolula Valley shifted, abandoned the mountaintop sites, and developed large population centers exclusively on the piedmont.

New agricultural techniques such as retention walls and terraces were adopted to keep up with increased population demands. Interregional commerce had well been established.

Settlement expanded during the Natividad phase (A.D. 900/950 – 1520/1535) in the

Valley of Teposcolula.

Previous sites on high elevated ridges and hilltops were still occupied, but generally remained small in size and population. Settlement preference shifted to lower elevations. The Teposcolula Valley became one of the largest populated areas in the

Mixteca Alta. The majority of the settlements were hamlets or small villages (117)

(Stiver, 2001:185). Thirty-three large villages, 12 small towns, and 4 large towns were identified (Stiver, 2001:185). Extremely valuable to manage agricultural resources, thousands of soil retention walls and terraces were constructed across the valley (Stiver,

2001:185).

El Fortin (TE 2)

El Fortin reached its peak in the Late Formative. This site is situated 200 meters above the historic trail from the Nochixtlan Valley entering the Teposcolula Valley

13 (Stiver, 2001: 124). There are a total of eight structures identified but several mounds and plazas have suffered post-depositional degradation. Ceramic artifacts that were recovered are gray ware which has also been found as offerings at Monte Alban (Stiver, 2001:125).

The estimated population is roughly 500 inhabitants. During the Classic Period population tripled and two additional structures were constructed. Ceramic assemblages incorporated Thin Orange ware from Teotihuacán (Stiver, 2001: 167). During the

Postclassic El Fortin increased to 45ha but estimated population decreased dramatically to 476 inhabitants (Stiver, 2001: 178). Bifacial production debris was found in abundance and 69 chert points and knife fragments were recovered. A total of 78 obsidian artifacts were recovered half of which were gray obsidian blades (Table 2.2). Other lithic reduction sites have been described at Tixa Viejo and TE 146.

Table 2.2 Gray and green obsidian distribution at three sites in the Teposcolula Valley.

Gray Green

Site Number Area (ha) Blade Non-blade Blade Non-blade Total

TE 1 289.25 316 174 265 79 834 TE 2 45.88 40 14 22 2 78 TE 127 116.13 39 91 53 109 292

Tixa Viejo (TE 127)

Tixa Viejo experienced a population increase in the Classic Period with a corresponding increase in public and domestic architecture (Stiver, 2001: 160). Classic architecture included mounds, platforms, and residential terraces. Tixa Viejo is

14 recognized as a political administrative center in the southwest portion of the valley

(Stiver, 2001: 163). In the Postclassic Tixa Viejo experienced another significant settlement expansion encompassing 1.2 square kilometers with an estimated population exceeding 1,000 inhabitants. Much of the Classic Period architecture was re-used. A total of ten structures were in use during the Postclassic. Modern day and colonial accounts record Tixa Viejo as a major salt production site. In fact, the Tixa Viejo area is the only region in the Mixteca Alta where evaporates occur. Reduction debris and unfinished bifaces were notable among the lithic assemblage. The assemblage included 36 chert tools and 292 gray or green obsidian blades and debitage (Table 2.2).

It should be noted that political tension between Tixa Viejo and Yucuninde was likely during the Classic Period. At the beginning of the Classic Yucuninde politically dominated the Teposcolula Valley (Stiver, 2001: 169). Political success at Yucuninde was short-lived in the Classic and this site does not reemerge in the Postclassic. Success at Yucuninde during the Classic may be attributed to the site’s strong affiliation with the political success in the Nochixtlan Valley which suffered collapse during the Postclassic

(Plunket, 1983; Spores, 1972)

Pueblo Viejo (TE 1)

Construction at Pueblo Viejo began in the Late Classic period, but with a population estimate of only 50 inhabitants the dramatic population increase in the

Postclassic overprinted evidence of earlier structures. During the Postclassic Period

Pueblo Viejo was as large as 2.5 square kilometers encompassing over 7,000 inhabitants.

The site is divided into five zones. Zone 1 is the only area with evidence of occupation in the Classis Period. Pueblo Viejo experienced a major expansion in the Postclassic and

15 Zone 1 became the main elite occupation center. Defense and retention walls surround

Zone 1 limiting outside access. Elite burials were excavated in association with Zone 1 further supporting political and economic importance at this site.

Pueblo Viejo stood out as a major city. This site accounted for 36 of 161 of the mounds and platforms found to be in use during the Natividad Phase (Stiver, 2001:188).

In addition to platforms and mounds primarily constructed in the Natividad, at least seven plazas were in use. With so many public structures, Pueblo Viejo was unmistakably an administrative center (Stiver, 2001:194). Archaeologists have identified several zones of occupation surrounding the ridge top. Other smaller, less dense, or less nucleated components either mimic or compliment the architecture at Pueblo Viejo linking the smaller sites to the suggested capital of Pueblo Viejo (Stiver, 2001:201). Architecture at other sites suggest likely roles in the valley’s economy such as secondary administrative centers, management for the valley’s agricultural production, and religious shrines

(Stiver, 2001:202). It is clear in the Natividad Phase the valley became well established and hierarchical systems were well developed.

The artifact assemblage reflects the valley’s participation in the long-distance trade network. The well represented ceramic artifact assemblage contains utilitarian items decorated with characteristics unique to the Teposcolula Valley. A large local production of ceramic goods was likely (Stiver, 2001:206). Exotic polychrome vessels and sherds were found in bulk at Pueblo Viejo and scattered at other sites. This costly trade good marked noble status, but may have been gifted to lesser ranked community members

(Stiver, 2001:207). Other wares specifically associated with the Aztec empire were found exclusively at Pueblo Viejo (Stiver, 2001:207). Other exotic artifacts such as jade beads

16 and shell are present in the artifact assemblage. The greatest amount of obsidian artifacts

(n= 834) were found at Pueblo Viejo (Table 2.2). Roughly 70% were blades of gray or green obsidian. Chert projectile points, knives, and scrapers at Pueblo Viejo were used, but to a far lesser extent.

Conclusions

Trade goods circulating from Monte Alban to the Valley of Teposcolula (and vice versa) would pass through the Nochixtlan Valley. Additionally, El Fortin and Yucuninde both had ceramic and lithic artifacts associated with the Valley of Oaxaca during Classic

Period occupation. Byland and Pohl (1994) interpret Mixtec occupation in the

Teposcolula Valley to be consistent with large-scale centralization akin to the Zapotec state in the Valley of Oaxaca. Multiple competing polities would increase feasting, warfare, and production of prestige goods, but these polities are also limited by agricultural sustainability (Blanton et. al., 1996). At Pueblo Viejo evidence of the importance of warfare and protection is found in the 2km defense wall, obsidian blade production, and agricultural centralization. In the Late Classic the Monte Alban state focused internally and political presence was lessened in adjacent valleys (Balkansky,

1998; Hutson, 2002; Marcus and Flannery, 1996). Sites in the Teposcolula Valley with strong alliances with Monte Alban did not fair well in the Classic to Postclassic transition. Yucuninde, which was previously mentioned to be in conflict with Tixa Viejo, suffered collapse and was abandoned in the Postclassic. El Fortin also experienced severe population decline. Since this site is situated where the Nochixtlan and the Teposcolula valleys meet continued occupation would have been advantageous particularly during

17 times when defensive positions were preferred. Many sites in the Teposcolula Valley

appear to have been partially abandoned by the Postclassic period (Stiver, 2001: 264).

Tixa Viejo is the only site positively identified to have had continued occupation from the Classic to the Postclassic (Stiver, 2001). It is likely that isolated salt production in the Mixteca Alta provided inhabitants sufficient subsistence goods through trade alliances with the Oaxacan coast and adjacent valleys such that occupation could continue at Tixa Viejo. Moreover, chert artifacts recovered suggest exchange networks

within the Nochixtlan Valley likely originating from Yucunudahui.

A large labor force was needed to construct the buildings and plazas at Pueblo

Viejo. Ritual items like censers were found at varying socioeconomically differentiated houses. Houses also contained a similar barrage of cooking implements unique to the

Teposcolula area (Stiver, 2001). Obsidian and chert tools were found, but the distribution of these artifacts throughout the site was not well documented. Both ritual items as well

as standardized cooking ware could likely have been adopted through the practice of a new social identity unique to Pueblo Viejo. A diversity of foreign polychrome wares were also recovered which could represent the remnants of previous social alliances.

Lithic production in the Teposcolula Valley was ubiquitous at least on a small

scale or as a part-time handicraft. Even though lithic production in Teposcolula did not

rival that of Teotihuacán or El Palmillo, it was important to exchange for other goods.

More details regarding spatial distribution of artifacts at the site level, detailed

descriptions of tool types, and provenance information would elucidate more information

regarding the importance of long-distance trade and supplemental local handicraft production.

CHAPTER THREE

GEOLOGICAL SETTING

The geology of Oaxaca, Mexico is quite complicated and is generally poorly

understood. The entire state of Oaxaca outlines three very distinct terranes representing

collisional and metamorphic events blanketed by a common sequence of Cretaceous

shallow marine carbonate rocks, Tertiary sandstones, and volcanic rocks. The goals of

this section are to 1) briefly review the tectonic evolution of Oaxaca, 2) briefly discuss

widespread geological units of interest, and 3) focus on the stratigraphy of four proposed

quarry sites.

Tectonic Setting

Oaxaca is located in an area of Mexico referred to as the Sierra Madre del Sur.

River systems in Oaxaca drain the Trans-Mexican Volcanic Belt and the area is

considered a basin and range style structure (de Cserna, 1989:257, Sedlock et al,

1993:68). Several terranes make up the Sierra Madre del Sur (Figure 3.1). The Cuicateco

terrane to the east of the study area and further toward the Gulf Coastal Plain, represents continuation of the fold and thrust belt of the Sierra Madre Oriental. The contact between the Zapoteco terrane and the Cuicateco terrane extends NNW-SSE through Oaxaca de

Juarez. Trending similarly, the contact between the Mixteco and Zapoteco terranes dissects the study area.

To the west, the oldest unit in the Mixteco terrane is the Acatlan Complex. The

Acatlan Complex represents deposition and metamorphism spanning Cambrian to

Devonian time (de Cserna, 1989:258, Sedlock et al, 1993:35). This approximately 15 km thick sequence includes schist, granite, gabbro, and ophiolite unconformably overlain by

Figure 3.1 (A) Location of the study area. (B) The Sierra Madre del Sur is delineated by the dotted line and continues south to the coast. Tectonostratigraphic terranes comprising southern Mexico include: Ju- Juarez terrane (Cuicateco), Gr- Guerrero terrane, Ma- Maya terrane, Mt- Mixteca terrane, Ox- Oaxaca terrane (Zapotec), Xo- Xolapa terrane. (C) The Sierra Madre del Sur expanded from box B and the location of paleogeographic units and major structures obtained from maps and texts used in this work. The location of the field areas referenced in this study follow: 1. Hernandez- Romano, (1997), 2. Garza, (2003), 3. Böhnel, (1999), 4. Ferrusquia, (1971), 5. Alaniz- Alvarez et.al., (1994), 6. field area for this study (refer to Figure 3.4), 7. Urrutia and Ferrusquia, (2001) (modified from Nieto-Samaniego et. al., 2006).

Mesozoic and Tertiary rocks. The Paleozoic deposits are associated with a subduction event followed by collision with the Zapoteco terrane by the Early-Middle Devonian

(Centeno et. al., 1999; Pantoja et. al., 1967; Sedlock et al, 1993:35). To the east, the oldest unit in the Zapoteco terrane is the Oaxacan Complex composed of Precambrian granulites. These granulites and associated metamorphic rocks represent a rifting event and show evidence linking the unit to Eastern North America (de Cserna, 1989:258).

Paleozoic strata include shale, sandstone, and carbonate rocks. This terrane is

20 unconformably overlain by Mesozoic rocks (similar to the Mixteco terrane) dominated early by carbonate rocks showing a closure in the ocean basin trending E-NE to W-SW.

There are also Cretaceous volcanic rocks of andesitic composition suggesting the presence of an island arc or a volcanic arc. In the Cenozoic, continental clastic sediments were derived from basement rocks. Oligocene volcanic rocks blanket the area (Martiny et. al., 2000; Moran et. al., 1998).

Geology of the study area

Basement rock assemblages in the study area are either the Acatlan Complex to the west or the Oaxcan Complex in the east. Mesozoic strata uniformly and unconformably overlie both basement complexes. The oldest overlapping rocks on the two different complexes are Jurassic deposits. These deposits include carbonate rocks interbedded with sandstone, siltstone, and mudstone (Böhnel, 1999; Nieto et. al, 2006;

Urrutia and Ferrusquia, 2001).

North of the study area the second deepest explored cave system in Mexico,

Sistena Cheve, is accessible. The explored depth is 1,386 m and the length is 23.3 km

(Hose, 1995). The Sistema Cheve formed in a belt of Cretaceous carbonate rocks approximately 4 km wide. The described deposits are similar to Cretaceous deposits observed in the field; “rudist-bearing limestone, laminated micrite, fore-reef breccia, thick to massive bedded dolomite, thin bedded limestone and chert, thin bedded limestone, laminated back-reef limestone, and mylonitic marble,” (Hose, 1995).

Throughout Oaxaca, lower Cretaceous deposits are found in contact with Jurassic sedimentary continental and marine rocks, the Acatlan Complex, or the Oaxacan

Complex (Böhnel, 1999; Nieto et. al, 2006; Urrutia and Ferrusquia, 2001). Argillacous

21 limestone (Mapache Formation) that overlies Jurassic sedimentary rocks near the Tepexi-

Tehitzingo basin north of the study area has been dated to the Late Jurassic to Early

Cretaceous (Böhnel, 1999). Similarly, Early Cretaceous deposits in the Tlaxiaco basin

(Zapotitlan Formation) consist of interbedded shale and thinly bedded argillacous

limestone (INEGI, 1984; Nieto et. al, 2006). Tight chevron folds are indicative of the

Zapotitlan Formation (Figure 3.2).

Figure 3.2 Chevron folds in the Zapotitlan Fm.

Early Cretaceous deposits are primarily carbonate rocks and are abundant in the

study area. Most of the deposits loosely correlate to carbonate rocks in states adjacent to

Oaxaca. Deposits include grainstone, packstone, wackestone, recrystallized micrite, and

interbedded with mudstone (Böhnel, 1999; INEGI, 1984; Hernandez, 1997; Molina et.al.,

2003).

In the Guerrero-Morelos platform (Figure 3.1), the Morelos Formation is roughly

800 m of shallow marine limestone and dolomite discordantly overlying the Mapache

Formation (Böhnel, 1999; Hernandez, 1997; Molina et.al., 2003). Urrutia and Ferrusquia

(2001) also describe 800 m of Cretaceous deposits near Oaxaca de Juarez. Shallow

22 marine facies are represented by bioclastic and pelliodal packstone and wackestone

interbedded with mudstone (Molina et.al., 2003). Ostracods, pelecypods, and benthic

foraminifera suggest an Albian-Cenomanian age (Böhnel, 1999; Hernandez, 1997;

Molina et.al., 2003; Urrutia and Ferrusquia, 2001).

In the Tlaxiaco basin the Teposcolula Formation is a massive bedded, rudist-

bearing limestone and chert found in transitional contact with lower Cretaceous deposits,

the Zapotitlan Formation (INEGI, 1984; Nieto, 2006). Near the modern town of

Teposcolula and archaeological ruins of Pueblo Viejo, the Teposcolula Formation is

currently mined for construction purposes. This formation was found to have an

abundance of milliolids and pelecypods (Figure 3.3) dating to the Albian.

Figure 3.3 Milliolid in the Teposcolula Fm.

Bar = 250µm.

The Orizaba Formation crops out in the Cordoba platform and also dates to the

Albian (Nieto et. al., 2006). Grainstone and packstone comprise this formation and are privy to dissolution and the formation of karsts. Radiolaria, sponge spicules, and milliolids dominate the fossil record in the Orizaba Formation.

23 Late Cretaceous deposits are thinly bedded with increased clay content interbedded with shale and sandstone in the upper part of the deposits (Hernandez, 1997;

Urrutia and Ferrusquia, 2001). Thickness of Late Cretaceous deposits (Tlaxiaco

Formation or Mezcala Formation) ranges 300- 400 m (Urrutia and Ferrusquia, 2001).

Unconformably overlying the Oaxacan Complex is the Tlaxiaco Formation

(Figure 3.4) (Nieto et. al, 2006; Urrutia and Ferrusquia, 2001). The Tlaxiaco Formation

corresponds to the Mezcala Formation cropping out in the Guerrero-Morelos basin

(Hernandez, 1997; Molina et.al., 2003). Both these formations are dated to the Turonian-

Maastrichtian (Molina et.al., 2003; Nieto et. al, 2006). Both formations are described as

marly limestone or interbedded calcareous mudstone and limestone (Molina et.al., 2003;

Urrutia and Ferrusquia, 2001).

Cenozoic rocks include Tertiary limestones, sandstones, siltstones, and

conglomerates with clasts of volcanic and carbonate rocks. These sedimentary deposits

are derivatives of the basement strata and are comprised of a combination of quartz, feldspars, and micas. Much of the matrix in conglomerate deposits consists of carbonate grains or glauconite. Some deposits show presence of iron oxide. Gypsum is commonly found throughout the Tertiary deposits.

The Tertiary Tamazulapan Conglomerate discordantly overlies the Cretaceous

Tlaxiaco Formation. This conglomerate consists of large well-rounded cobbles up to 10 cm in diameter (INEGI, 1984). Clasts include carbonates, andesite, basalt, and chert.

Thickness ranges 30 to 80 m (Böhnel, 1999; Urrutia and Ferrusquia, 2001). The

Yanhuitlan Formation discordantly overlies the Tamazulapan Conglomerate. The

24 rtiary and Cretaceous units (1999), C. Nieto-Samaniego and others, of several chert bearing Te lex. Multiple representations of the stratigraphy of the of the stratigraphy representations lex. Multiple E. this study. (see also Figure 3.1). e Teposcolula Valley consists the following: A. Böhnel, (1999), B. Figure 3.4 The stratigraphy in th Figure 3.4 The overlying earlier Mesozoic deposits and the Oaxacan Comp deposits earlier Mesozoic overlying valley from NW to SE (2006), D. Urrutia and Ferrusquia, (2001),

25 Yanhuitlan Formation consists of alternating red and beige subarkoses (Ferrusquia,

1971). Grain size ranges from silt to fine sand, but clay and carbonate matrix are also abundant. Thickness of the Yanhuiltan Formation is estimated at 400 meters (Ferrusquia,

1971). Gypsum deposits occur in the Yanhuitlan Formation.

Tertiary andesite, ashes, and tuffs of intermediate to acidic composition cap

Tertiary clastic sedimentary deposits (INEGI, 1984). Interbedded with the upper portion of Tertiary andesite, the Chilapa Formation is 350- 400 m of medium-bedded silicified limestone (Ferrusquia, 1971). Peat lenses and clastic sediments are found occasionally interfingered with limestone. Chert nodules and lenses are more commonly found interbedded with limestone. The Chilapa Formation corresponds to the limestone member in the Suchilquitongo Formation cropping out in the Valley of Oaxaca (Ferrusquia,

1971). The Suchilquitongo Formation also includes an ignimbrite member overlying white silicified limestone of approximately Miocene age (Urrutia and Ferrusquia, 2001).

Quarry Stratigraphy

Yolomecatl

The quarry of Yolomecatl (YOLO) is located approximately 7 km west of

Teposcolula (Figure 3.5). Along the side of a dirt road leading to a privately owned farm, the Teposcolula Formation was exposed (Figure 3.6). Sparse vegetation grew where weathering of the limestone resulted in caliche deposits. Dark brown to black chert lenses or nodules were interbedded with recrystallized limestone. Samples were extracted from lenses of chert ranging 0.01 – 0.1 m in thickness and several meters in diameter. The sampling area was approximately 7 m laterally along the road and from multiple chert horizons in 2 meters of a vertical section within the Teposcolula Formation.

xteco to the west and tween two terranes, the Mi odified from INEGI, 1984). Figure 3.5 The study area is divided by the contact be Figure 3.5 The the Zapoteco to east (m

Figure 3.6 The hillside outcrop at Yolomecatl exposes the Teposcolula Fm. and chert-rich layers (1 meter scale).

Chilapa del Diaz

The modern city of Chilapa del Diaz is located 13 km northwest of Teposcolula

(Figure 3.5). Around Chilapa del Diaz the tightly folded Tlaxiaco Formation was observed in contact with the Yanhuitlan Formation. The Chilapa Formation discordantly

overlies the Yanhuitlan Formation. Approximately 3 m of the Chilapa Formation was

exposed at a fresh road cut (Figure 3.7). Some silt, clay, and silica-rich layers were

interbedded with limestone. Bed thickness of limestone was less than 0.5 m. Chert

nodules were sampled from multiple horizons of silicified limestone in the Chilapa

Formation. Chert from more than one section in the Chilapa Formation was sampled

along Highway 190.

San Felipe Ixtapa

The quarry of San Felipe Ixtapa (SFI) is located approximately 4 km west of

Teposcolula along Highway 125 (Figure 3.5). An entire hillside exposed the Cretaceous

Teposcolula Formation (Figure 3.8). Brush and trees partially covered the outcrop. Dark brown to black chert lenses or nodules were interbedded in recrystallized limestone.

Samples were extracted from lenses of chert ranging 0.01 – 0.1 m in thickness and

28 Chilapa Formation

Limestone

Chert nodules at 2m

Limestone

0.1m of silt

0.4m of sand

Limestone

Figure 3.7 A fresh road cut exposes 3m of the Chilapa Fm. near the modern town of Chilapa del Diaz.

Figure 3.8 The hillside exposure of Cretaceous limestone and chert-rich layers at San Felipe Ixtapa.

several meters in diameter (Figure 3.9). The sampling area was approximately 7 m laterally along the base of the hillside and 2 m vertically. Remote and condensed pits with increased limestone and lithic debitage may be the only evidence that this outcrop was once used to extract chert for stone tools (Figure 3.10)

Figure 3.9 Chert-rich layers in the Teposcolula limestone were several centimeters thick at San Felipe Ixtapa.

Figure 3.10 A possible testing area for flint knappers in antiquity littered with chert debitage at San Felipe Ixtapa (1 meter scale).

Prieto

Seventeen kilometers east-northeast of Teposcolula and Highway 190 near the

modern town of Nochixtlan the quarry of Prieto (PRI) is accessible by foot. Along the

path leading up to the summit of the mountain, the siltstones of the Yanhuitlan Formation

were observed. The contact between the Yanhuitlan Formation and the Chilapa

Formation was not observed, but at the summit of the mountain, the Chilapa Formation

containing large cobble sized chert nodules had been reduced to a cache of chert.

Samples were collected as “grab” samples from the heap of quarry debris at the summit

of Prieto (Figure 3.11). The sampling area was approximately 5 square meters.

Figure 3.11 A preliminary testing site for chert cobbles extracted from the Chilapa Fm. at Prieto (1 meter scale).

Summary

The quarries of Yolomecatl and San Felipe Ixtapa are both located due west of the archaeological site Pueblo Viejo. Chert from both these quarries was extracted from the

Cretaceous Teposcolula Formation. Chert from the quarries of Chilapa and Prieto were extracted from the same limestone host rock, the Tertiary Chilapa Formation. I expect

similarities in chemistry, fossil constituents, and isotope values to exist in chert from the

quarries of Yolomecatl and San Felipe Ixtapa. Likewise, similarities should exist between

Chilapa and Prieto. I also anticipate differences in chemistry, fossil constituents, and

isotope values to exist in chert from the Cretaceous limestone formation versus chert

from the Tertiary limestone formation.

CHAPTER FOUR

CLASSIFICATION AND PROPERTIES OF CHERT

Historically, archaeologists have identified chert based on knapability or the

ability of a given sample to be fashioned into a tool and, to a lesser extent physical

properties (e.g. color and luster) (Goodman, 1944). Classifications of chert stem from

these physical properties and are commonly named for local geographical areas where

samples are obtained. Many problems arise from this overly simplified method. A single

outcrop of chert can vary considerably in physical properties from the base of the

sequence to the top. Regionally, a rock layer containing chert may crop out multiple times and each outcrop and/or quarry site may have several common names.

Unfortunately many deposits of quality chert exist in the study area. When given two

nearly identical samples of chert from two different geographic and geologic locations

my guide don Benito, a local Oaxacan flint knapper from Teposcolula correctly identified

the origin of each sample based on his “assessment of quality”. Unfortunately, field

archaeologists and geologists lack this local knowledge and primarily rely on good

descriptions of chert based on physical properties.

Formation Processes and Varieties of Chert

The specific nature of chert formation is poorly understood. It is known that

authigenic silica forming chert can be produced biogenetically and later altered

diagenetically (Knauth, 1994:237). Replacement chert is commonly associated with

carbonate deposits. These deposits provide the biogenic factors necessary for opal-A

production and alteration to microquartz. Modern silica production is driven by diatoms.

Diatom oozes composed of opal-A are deposited in shallow marine beds and later

32 converted to opal-CT and then to microquartz. Silica deposition in this case would be confined to coastal environments with microquartz transformation occurring in the mixing zone of marine and fresh water. Diatoms have only been a mechanism of chert formation for the past 50 million years and while the pathway of opal-A to microquartz formation can be seen in deep sea cores, any evidence of an opal precursor in ancient cherts would be overprinted.

Knauth (1994) combined limiting factors and evidence for silica precipitation from previous research into a comprehensive scenario for nodular chert formation. To summarize, carbonate grains and siliceous sponge spicules coexist in sediments of nearshore mixing zones. Following sediment burial, meteoric waters stabilize carbonate through solution/re-precipitation and opal-A dissolves. Quartz precipitation from groundwater occurs when silica concentration exceeds 4ppm. Nodules are anticipated to form along areas of greatest groundwater flux (Figure 4.1). The two biggest limiting factors for the precipitation of chert are 1) silica concentration of water and 2) accommodation space for crystal growth.

Figure 4.1 This schematic represents permeable carbonate deposits at near shore mixing zones and interaction with meteoric water contributing to the formation of chert (from Knauth, 1994).

33 Bedded or Ribbon Chert

In the Mesozoic, Radiolarian produced bedded chert deposits deepsea basins. It is

also possible that cherts formed by direct precipitation of microquartz (Dietrich, et. al,

1963; 663). These deposits are associated with subduction zones where hydrothermal

fluids enriched in silica directly precipitate silica. These deposits are named ribbon cherts

after the pinch and swell structure of the beds. Novaculites are very similar to ribbon

cherts, but are commonly pure white.

Nodular or Replacement Chert

Nodular cherts are a common diagenetic feature of platform carbonate rocks.

Nodules range in size from cm-sized oblong blebs to meter-sized lenses (Knauth, 1994;

244). Mechanisms of replacement have not been fully constrained for nodular cherts.

Early views asserted silica precipitated as gels rolling along sea floors in masses then

converted to quartz through burial (Tarr, 1917). Later authors attributed silicification of

carbonates to an increase in solubility of calcite from the thermodynamic ability of quartz

and exerted pressure of crystal growth (Biggs, 1957; Dietrich, et. al, 1963; Maliva, 1988).

In Knauth’s (1994) model, nodular chert precipitation is restricted to near shore mixing zones under shallow burial conditions.

Physical Properties

Microscopically, three crystalline varieties of chert have been identified; granular microcrystalline quartz, fibrous silica, and megaquartz (Knauth, 1994:234).

Microcrystalline quartz, a fine grain quartz ranging 1 to 50µm in size and is the most

common crystalline variety of chert. Average grain size of ancient cherts ranges from 8 to

10 µm. Fibrous silica is more commonly known as chalcedony and forms botryoidal

34 arrays filling fractures, cavities, and vugs. Chalcedony tends to precipitate from waters

that are Mg-rich or in the presence of sulfates. Megaquartz grains are well developed

quartz crystals larger than 50µm and precipitate out of solution generally filling vugs and

cavities indicating slower crystal growth. Microquartz can be recrystallized to megaquartz (Knauth, 1994:237). The presence of megaquartz is commonly interpreted as representing declining silica concentrations or decreasing fluid flow and slower crystal growth.

Knauth’s (1994) model for the precipitation of silica phases suggests a linkage between phases. The relative abundances of each phase are controlled by water depth and hydrological activity and are limited by compaction, burial, and temperature (Figure 4.2).

All three phases can be precipitated at varying times during diagenesis as hydrological

Figure 4.2 A general diagram of the pathways in which chert can form and the factors limiting formation (from Knauth, 1994).

35 activity fluctuates. There is a genetic linkage in siliceous oozes when opal-A converts to opal-CT and then to microquartz under increasing burial and temperature. Similarly, microquartz can be metamorphosed to megaquartz.

Archaeologists use five properties to distinguish cherts; 1) texture, 2) luster, 3) color, 4) fossil constituents, and 5) structural characteristics (Goodman, 1944; Luedtke,

1992). Texture refers to grain size where coarse grains are visible to the naked eye, medium grains require a low power (10- 15x) hand lens, and fine grains are visible under higher (200x +) power magnification. Luster is described as dull, waxy, or vitreous.

Munsell color charts are used as references to describe color. Common coloration of cherts range from off-white to black, but pink hues, red jasper, and colorless chert, are also common. Fossils while sparse and poorly preserved may include bivalves, sponge spicules, crionoids, and bryozoa. Structural characteristics include properties such as vugs or cavities, oxidation, banding, or flecked or speckled patterns.

Chemical Properties

Quartz is considered a framework silicate or tectosilicate. Beginning with the basic tetrahedron which has one cation and four O-2 anions, a tectosilicate then adds four more tetrahedral that each share one O-2 anion with the initial tetrahedron creating a three-dimensional framework (Figure 4.3). Because accommodation space within each tetrahedra is increased by sharing anions, larger cations such as Na+, K+, Mg+2, and Al+3 can be incorporated into the tetrahedron. The ideal cation for the tectosilicate crystal structure is Si+4. Any deviation from the ideal crystal structure increases instability.

Replacing some Si+4 cations with Al+3 for example will not completely change the resulting rock type, but will effectively create weaknesses on the molecular level

36 ultimately affecting the knappability or quality or the chert. The environment and conditions under which chert is formed are the limiting factors for the replacement of Si+4 in the crystal lattice. The common host rock carbonate and interstitial waters can introduce a breadth of elements to the formation process of chert, but not all of these components can fit in the framework.

Figure 4.3 Framework silicates consist of one Si+4 and

four O-2 in a three-dimensional tetrahedron.

Water trapped as fluid inclusions or released from Si-O bonding contributes between 0.2 and 2.0wt% of a given chert sample (Knauth, 1994:234). Oxygen and deuterium values can be measured from the trapped fluids. These values reflect the conditions during the formation of the chert and diagenetic events following formation.

Deuterium values are generally 50‰ depleted relative to the water in which chert formed and 30‰ enriched in 18O (Gao and Land, 1991; Knauth, 1994). Water in fibrous silica or chalcedony is typically structural OH and 1 to 2wt% of a given sample (Knauth,

1994:234).

CHAPTER FIVE

METHODS

Over 100 samples were collected from each quarry. All samples from Yolomecatl and San Felipe Ixtapa were extracted from host Cretaceous carbonate rocks of the

Teposcolula Fm. Samples from Chilapa were extracted from Tertiary carbonate rocks.

Only one quarry, Prieto (PRI), samples were collected as ‘grab’ samples of quarry debris from the outcrop of Tertiary carbonate host rocks. When possible, the same sample was used for multiple techniques (see Appendix A). This section will review the different analytical techniques applied in this study.

X-Ray Diffraction

X-Ray diffraction (XRD) is used to identify minerals in complex mineral assemblages. The X-rays are diffracted by atomic planes within the mineral and their intensity is measured by a detector (Stanjek et. al., 2004). Structure of crystalline minerals is determined by positions and intensities of diffraction peaks.

Pretola (2001) used XRD to identify silica polymorph ratios of chert in order to source lithic materials. Chert is composed of varying amounts of silica polymorphs quartz and moganite. Both chert and chalcedony contain percentages of quartz and

moganite said to be unique to a deposit (Pretola, 2001).

Two samples were selected from each quarry for XRD analysis at the University

of Georgia with a Scintag XDS2000 X-Ray diffractometer using Co Kα radiation.

Samples were crushed into a fine powder using a corundum mortar and pestle and then

ground in a tumbler with corundum pellets and ethanol. Samples were dried for 24 hours.

All equipment was thoroughly washed between samples to avoid contamination. Next 3g

38 of dry powdered sample was pressed into a small 1 in2 sample frame for analysis (see

Appendix B).

Petrography

Petrography is used to identify crystal phases of chert, fossil constituents, and other microscopic occurrences. Representative chert samples from each quarry were initially cut and polished at the University of Georgia. When possible, carbonate cortex on a silicate sample was included in the area to be thin sectioned. Other non-silicate samples were also thin sectioned to discern stratigraphic relationships between quarries.

All samples were sent to Vancouver Petrographics for final thin section preparation.

Hydrofluoric Acid Treatment

Eighty representative samples from four different sources were selected for an etching treatment with hydrofluoric acid initially adopted by Pessagno and Newport

(1972) to extract radiolarian from cherts (see also Pessagno and Yang, 1989; Pessagno and Meyerhoff, 2002). In this study, etching describes a dissolution process of the surface and not the entire sample. Two treatments were run with concentrated of HF acid; the first batch of samples was submerged in a HF bath for four minutes, the second batch for ten minutes. After etching, samples were rinsed in a water bath for twenty minutes, and dried. Samples were then inspected with a low magnification dissecting microscope for different silica phases and preserved fossils.

Electron Microprobe Analysis

Thin sections were prepared from 10 representative samples from each quarry source, forty total. Samples were cut, polished, and mounted to glass slides. The excess sample was cut from the section and slides were hand polished to 1000µm finish using

39 aluminum oxide grit. Samples were then thoroughly washed to expel residual aluminum to avoid contamination. Diamond paste was used next to polish samples to a 0.25µm finish. Sample size varied between one to two centimeters squared. Polished and carbon

coated, each sample was analyzed for a basic suite of ten elements including Si, Ti, Al,

Mg, Fe, Mn, Ca, K, Na, and Cu. Thirty points, dispersed over the entire sample surface

were measured on each sample. Due to sample preparation complications such as broken

slides and samples cut too thick, not all forty samples were analyzed.

All samples were analyzed with a JEOL 8600 electron microprobe (EMP) at the

University of Georgia. Natural and synthetic minerals were used for daily calibration.

Wave length dispersive (WDS) analyses were done with an electron beam current of

15nA with and acceleration voltage of 15keV. Spot size was 10 microns. Counting time

was 10 seconds on peak and background. A secondary standard of quartz was used, but

only reflects precision for silica.

Minimum detection limits varied for each element and varied from day to day

(see Appendix C). The range of minimum detectable limits of SiO2 for example was

0.05-0.054±0.001wt% (refer to Chapter 6). Totals for each analysis generally do not

equal 100%, probably due to trapped water in the chert.

Stable Isotopes

All chert samples were analyzed for stable isotopes at the University of New

Mexico. δD values were determined using a lengthy preparation protocol and mass

spectrometry (Sharp, 1990; Sharp et. al., 2001). The technique is capable of measuring

very small amounts of material (<0.1µl of water for δD). The precision of the procedure

40 for water samples is ±2‰ (1σ) for hydrogen (Sharp et. al., 2001). Water present in

silicate is either structural or trapped inclusions.

Solid samples are reacted with glassy carbon at high temperatures (1450°C), H2 and CO2 are produced, separated with a gas chromatograph, and analyzed with a

Finnigan Mat Delta XL Plus mass spectrometer.

To obtain δ18O values a laser-based method was employed. A laser directly heats

samples as small as 100µm. The precision and accuracy are both ±0.1‰ (1σ) equivalent to conventional methods (Sharp et. al., 2001).

Samples are placed on a nickel sample holder in a stainless steel chamber and heated with a 20W CO2 laser through a window transparent to infrared and visible

radiation. This laser extraction technique uses BrF5 as a fluorinating agent. Oxygen

released is trapped in a cold finger trap, reacted with hot carbon, converted to CO2, and

measured with a Finnigan Mat Delta XL Plus mass spectrometer.

δ18O and δ13C values of host carbonate rocks were obtained at the University of

Georgia using a Finnagin Delta mass spectrometer (see Appendix D). When possible,

carbonate cortex from silicate samples also used for isotope analysis was analyzed.

Typically only 3mg of sample is required, but partial replacement of carbonate by silicate

necessitated using 5mg of sample. In vials powdered samples were dissolved with

phosphoric acid off-line at 50°C. CO2 gas was separated from the sample on a vacuum

line and measured and analyzed with a Finnagin Delta mass spectrometer. For routine

analyses error is 0.02‰ (1σ) for both δ18O and δ13C based on six separate vacuum line

preparations and mass spectrometer analyses. Two laboratory standards, FISHER and

A1296, were prepared and analyzed with each batch of samples. Both laboratory

41 standards have been calibrated with international carbonate standards RM 8544 (NBS-19 calcite) and RM 8543 (NBS-18 carbonate) in accordance with the National Institute of

Standards of Technology (NIST).

CHAPTER SIX

RESULTS

Physical Properties and Petrography

Quartz and chalcedony are easily distinguishable in thin section based on optical

properties. Crystalline quartz is colorless under plain light and show high pleochroism under cross polar light. Quartz also has undulatory extinction. Fibrous chalcedony is colorless and shows radiating concentric zones of extinction.

Yolomecatl

Yolomecatl samples were all fine grained. Samples were waxy to vitreous. Color ranged from black to brown to blue. Many samples had marbling effects of white opaque but vitreous chert.

Four chert samples from Yolomecatl were selected and thin sectioned for petrographic analysis (Table 6.1). Very fine grain microquartz (1 to 50µm) comprises 60-

95% of Yolomecatl chert samples. Minor amounts of chalcedony (5-30%) are also

present. Several samples have bands of insoluble material (e.g. clays and organics)

juxtaposed between microquartz. Sample YOLO-CH-48 has microquartz surrounding

large glassy material (Figure 6.1).

Chilapa

Chilapa samples were fine grained in texture. The luster ranged from dull to

waxy. Colors ranged in brown hues to white with a few samples slightly gray and even a

rosey color. Other characteristics included banding and speckling.

Five chert samples from Chilapa were selected and thin sectioned for petrographic

analysis (Table 6.1). Quartz phases in Chilapa samples are 30-90% microquartz and 50-

43 70% chalcedony. Two samples had minor amounts of megaquartz (2-5%). Large vugs

and veins are also filled with fibrous chalcedony. One sample, CHI-CH-67, revealed

patchy silicification of micrite similar to samples from Prieto (Figure 6.2).

Table 6.1 Thin section observations from four quarries.

1 Sample Megaquartz MicroQuartz Chalcedony Observations (+50µm) (1-50µm)

YOLO 43 0 60 30 Some clay YOLO 44 0 90 5 Some clay YOLO 48 0 70 10 Clay present in bands YOLO 24 0 95 5 Some clay

CHI 23 5 75 20 Vugs of chalcedony CHI 35 0 95 5 Some veins CHI 67 0 80 5 Some clay CHI 103 0 30 70 CHI 104 2 68 30 Some vugs

SFI 1A 3 90 7 Gastropod SFI 1C 5 50 45 Gastropod, chalcedony vugs/veins SFI 1D 1 90 9 Fossils, chalcedony vugs, muscovite SFI FB 0 95 5 Clay present, hematite SFI 1E 0 95 5 Gastropod, some clay SFI 1H 0 90-95 5-10 Chalcedony vein

PRI 8 1 89 10 Cache of bivalves, chalcedony veins PRI 9 0 20 30 Large amounts of clay PRI 17 0 20 30 Large amounts of clay, bivalves PRI 24 0 80 10 Large amounts of clay, bivalves PRI 49 0 60 10 Large amounts of clay, bivalves

1 Ratios of quartz phases in percentages based on microscopic observations

Figure 6.1 Microquartz growth isolated Figure 6.2 Microquartz and insoluble material to thin bands chalcedony are replacing carbonate between quartz crystals. Bar = 500µm grains. Bar = 500µm

San Felipe Ixtapa

San Felipe Ixtapa samples were all fine grained. Samples were waxy to vitreous.

Color ranged from black to brown to blue. Some marbling was also apparent.

Six chert samples from San Felipe Ixtapa were selected and thin sectioned for

petrographic analysis (Table 6.1). Quartz phases present include microquartz (1 to 50µm)

and chalcedony. Both the size and shape of microquartz grains is homogeneous ranging

from rounded grains approximately 0.04-0.01mm in size. Microquartz makes up 50-95%

of samples. Fibrous chalcedony makes up 5-45% of samples and was isolated to vugs and

veins and ranged in size from 1.0mm to 0.4mm. Minor amounts of megaquartz were also

present. A few preserved gastropods were identified in two samples.

Prieto

Samples from the quarry of Prieto were all fine grained and dull or waxy in luster.

Color in all Prieto samples ranged in brown hues and “café con leche” colors.

Five chert samples from Prieto were selected and thin sectioned for petrographic

analysis (Table 6.1). Thin sections revealed silicification of micrite in all samples.

45 Samples are 20-90% microquartz and 10-30% chalcedony. No megaquartz grains were

present in the selected samples and large amounts of clay characterized Prieto samples.

Bivalves are also replaced with silicate. In sample PRI-CH-17, there is a clear gradation

of microquartz silicification from the interior of the sample to the micrite cortex (Figure

6.3).

Figure 6.3 The interface between the chert (left) and the carbonate host rock is not clearly defined as microquartz replaced carbona te grains. Bar = 250µm

Hydrofluoric Acid Treatment

The ten minute samples confirmed the presence of ostracods specific to one

quarry. Several silica phases and growth patterns were observed. Most common was

microquartz. There were also large vugs and cavities of megaquartz and radial fibrous

quartz. Random megaquartz (≥50µm) crystals were also visible in samples treated with

HF but not in thin sections.

Yolomecatl

Twenty-two samples from Yolomecatl were treated with hydrofluoric acid. Two

samples were reacted for four minutes. Sample YOLO-CH-46 had a well-preserved

bivalve and several euhedral quartz crystals visible among fine grain microquartz (1 to

46 50µm) (Figure 6.4). Sample YOLO-CH-20 also reacted for four minutes, had traces of

hematite. The samples treated for ten minutes were mostly grainy microquartz with a few

bivalve fossils in several samples and cavities or vugs filled with chalcedony or

botroydial quartz. Some samples had fractures initially filled with fibrous quartz and later filled with granular quartz.

Figure 6.4 This well preserved bivalve was one of very few in hydrofluoric acid etched YOLO samples. Bar= 250µm

Chilapa

Twenty-two samples from Chilapa were treated with hydrofluoric acid. Two

samples were reacted for four minutes. The two samples reacted for four minutes had

round raised bloom-like features of microquartz. The samples reacted for ten minutes had

in general smooth surfaces with chalcedony filled fractures or less frequently isolated

megaquartz. A few samples had fractures or veins partially filled with chalcedony and

later filled with a more granular form of quartz.

San Felipe Ixtapa

Fourteen samples from San Felipe Ixtapa were treated with hydrofluoric acid.

Two samples were reacted for four minutes. Sample SFI-CH-FA had two well-preserved crinoids and traces of hematite. Sample SFI-CH-FB also had remnants of crinoid-like

47 fossils and a possible cross section of a large bivalve shell filled with chalcedony. The samples reacted for ten minutes were overall smooth in appearance with limited amounts of chalcedony. Most of the ten minute samples had minor amounts of hematite present

(Figure 6.5).

Figure 6.5 Minor amounts of hematite were observed in SFI hydrofluoric acid etched samples. Bar = 250µm

Prieto

Twenty-two samples from Prieto were treated with hydrofluoric acid. Two samples were reacted for four minutes. Sample PRI-CH-22 had round depression features and sample PRI-CH-1 had an abundance of bivalves preserved, most likely ostracods

(Figure 6.6). The ten minute samples also had an abundance of bivalves preserved. Some samples had cavities or vugs filled with megaquartz.

Summary

Quartz phases present in Yolomecatl samples primarily include microquartz with minor amounts of botroydial quartz isolated in vugs and cavities. Hematite also appeared in several samples. Chilapa samples consisted of microquartz with fractures filled with chalcedony. Quartz phases present in San Felipe Ixtapa samples included minor amounts of chalcedony. Similar to Yolomecatl samples, San Felipe Ixtapa samples have trace

48 amounts of hematite. Prieto samples can be confidently be distinguished by the vast

abundance of bivalve fossils present relative only to the other three quarries.

Figure 6.6 Abundant bivalves etched with HF acid in sample PRI-CH-1 were characteristic of that quarry. Bar= 500µm

Electron Microprobe Analysis

Detection limits for Electron Microprobe (EMP) samples varied slightly on a

daily basis for the most prevalent oxides, Al2O3, MgO, CaO, K2O, and Na2O (Table 6.2).

A quartz standard was analyzed on a daily basis and provides an estimate of error

associated with SiO2, but other elements were below detection limits (Table 6.3).

Yolomecatl

Nine Yolomecatl samples were cut and polished for EMPA analysis. Averages of

non-SiO2 oxides above detection limits did not exceed 1 wt% (Table 6.4). Yolomecatl samples had detectable amounts of both Al2O3 and MgO present in 11 points measured

from two samples. Aluminum oxide ranges from 0.18 to 2.21 wt % and MgO ranges from

0 to 0.17 wt % (Figure 6.7). When plotted, Yolomecatl samples with detectable amounts

of Al2O3, MgO, and CaO cluster with compositions roughly 70% Al2O3, 5% MgO, and

25% CaO (Figure 6.8). Only one point plots with a composition nearly 100% CaO. That

point at 4.41 wt%, is an inclusion of calcite.

49 Table 6.2 Daily Electron Microprobe Analysis minimum detection limits.

Sampling Day Oxide (wt %)

SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O

19-Jan 0.052 0.046 0.049 0.15 0.14 0.039 0.037 0.071 27-Jan 0.054 0.046 0.051 0.18 0.14 0.042 0.034 0.070 30-Jan 0.052 0.047 0.052 0.16 0.15 0.044 0.032 0.073 31-Jan 0.054 0.048 0.050 0.18 0.18 0.041 0.034 0.073 20-Feb 0.054 0.049 0.054 0.17 0.15 0.043 0.037 0.078 21-Feb 0.050 0.044 0.051 0.19 0.17 0.042 0.037 0.069

Mean 0.053 0.046 0.051 0.17 0.16 0.042 0.035 0.072 Standard Deviation ±0.002 ±0.002 ±0.002 ±0.01 ±0.02 ±0.002 ±0.002 ±0.003

Table 6.3 Daily EMP measurements of a quartz standard.

Sampling Day Oxide (wt %)

SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O

19-Jan 98.2 0 0.02 0.02 0.05 0.002 0.017 0 27-Jan 101.3 0.01 0.02 0 0 0.013 0 0 30-Jan 100.9 0.04 0.01 0.02 0.08 0 0 0.006 31-Jan 98.2 0.02 0 0.02 0.05 0 0 0 20-Feb 98.7 0.05 0 0 0 0.004 0 0.012 21-Feb 99.2 0.01 0.03 0 0.04 0 0.012 0

Mean 99.4 0.02 0.01 0.01 0.04 0.003 0.005 0.003 Standard Deviation ±1.3 ±0.02 ±0.01 ±0.01 ±0.03±0.005 ±0.008 ±0.005

50 Table 6.4 Average of points above EMP minimum detection limits for nine samples from the quarry of Yolomecatl.

Sample Oxide (wt %)

Al2O3 MgO CaO K2ONa2O

YOLO 24 0.76±0.4 0.07±0.03 0.27±0.16 0.13±0.07 0.07±0.03 YOLO 6 0.08±0.05 0.05±0.01 0.43±1 0.07±0.05 -- YOLO 20 0.09±0.05 -- 0.06±0.02 -- -- YOLO 12 0.11±0.07 -- 0.1±0.06 0.06±0.03 -- YOLO 43 0.07±0.05 -- 0.06±0.03 -- -- YOLO 9 0.13±0.08 -- 0.08±0.06 0.06±0.06 -- YOLO 11 0.08±0.06 -- 0.19±0.2 0.06±0.2 -- YOLO 34 0.09±0.06 -- -- 0.06± -- YOLO 44 0.09±0.05 -- 0.47±0.4 0.05±0.4 --

Mean ±Standard Deviation 0.17±0.22 0.01±0.03 0.18±0.17 0.05±0.04 0.01±0.02

MDL 0.05 0.05 0.04 0.04 0.07

0.16

0.14

0.12

0.1

0.08

0.06 MgO (wt%)

0.04

0.02

0 00.511.522.5

Al2O3 (wt %) Figure 6.7 Aluminum and magnesium oxide content from two samples representing the quarry of Yolomecatl.

MgOMg

0 100

10 90

20 80

30 70

40 60

50 50

60 40

70 30

80 20

90 10

100 0

CaOCa 0 102030405060708090100AlAl2O3

Yolomecalt Chilapa Prieto

Figure 6.8 Points from each quarry with measurable amounts of Al2O3, MgO, and CaO above minimum detection. Samples from SFI did not have measurable amounts of each element in any point analyzed.

52 Chilapa

Eight Chilapa samples were cut and polished for EMPA analysis. Averages of

non- SiO2 oxides above detection limits did not exceed 1 wt% (Table 6.5). Chilapa samples had detectable amounts of both Al2O3 and MgO present in 18 points measured

from only one sample. Aluminum oxide ranges from 0 to 0.25 wt % and MgO ranges

from 0 to 0.15 wt% (Figure 6.9). When Chilapa samples with detectable amounts of

Al2O3, MgO, and CaO were plotted, points clustered with compositions of nearly equal

proportions, but overlap points from the quarry of Prieto (Figure 6.8).

Table 6.5 Average of points above EMPA minimum detection limits for nine samples from the quarry of Chilapa.

Sample Oxide (wt %)

Al2O3 MgO CaO K2O Na2O

CHI 104 0.08±0.05 -- 0.06±0.01 0.04±0.02 -- CHI 67 0.09±0.05 0.08±0.02 0.11±0.07 0.07±0.02 0.11±0.02 CHI 26 0.08±0.04 -- 0.05±0.01 0.05±0.02 -- CHI 12 0.06±0.03 -- 0.06±0.02 0.04±0.02 -- CHI 103 0.19±0.1 -- 0.07±0.03 0.07±0.03 0.08 CHI 44 0.11±0.08 -- 0.12±0.1 0.06±0.02 0.1±0.03 CHI 39 -- -- 0.05±0.01 0.06±0.02 0.09±0.02 CHI 23 0.09±0.04 -- 0.04±0.01 0.04±0.01 0.07

Mean± Standard Deviation 0.09±0.05 0.01±0.03 0.07±0.03 0.05±0.01 0.06±0.05

MDL 0.05 0.05 0.042 0.035 0.072

53 0.14 0.12 0.1 0.08 0.06

MgO (wt %) 0.04 0.02 0 0 0.05 0.1 0.15 0.2 0.25

Al2O3 (wt %) Figure 6.9 Aluminum and magnesium oxide content from only one sample representing the quarry of Chilapa.

San Felipe Ixtapa

Six San Felipe Ixtapa samples were cut and polished for EMPA analysis.

Averages of non-SiO2 oxides above detection limits did not exceed 1 wt% (Table 6.6).

This quarry had the least amount of trace elements in the points analyzed. San Felipe

Ixtapa is the most homogeneous with respect to silica and does not have detectable

magnesium in any sample. When Al2O3, MgO, and CaO were plotted SFI samples were excluded because not one point had all three oxides above minimum detection limits.

Prieto

Eight Prieto samples were cut and polished for EMPA analysis. Of all averages of

non-SiO2 oxides above detection limits and only MgO and CaO exceeded 1 wt% (Table

6.7). This quarry did not have any detectable amounts of Na2O and appeared to have the

most even distribution of Al2O3, MgO, CaO, and K2O. Prieto samples had detectable

amounts of both Al2O3 and MgO present in 81 points measured from seven samples.

54 Table 6.6 Average of points above EMPA minimum detection limits for nine samples from the quarry of San Felipe Ixtapa.

Sample Oxide (wt %)

Al2O3 MgOCaO K2O Na2O

SFI 1A 0.05±0.04 -- -- 0.04 -- SFI FA 0.09±0.07 -- 0.07±0.05 0.02±0.05 0.18 SFI FB 0.1±0.08 -- 0.05±0.01 0.06±0.01 -- SFI 1K.4 0.13±0.10 -- 0.06±0.02 0.06±0.02 -- SFI 1E 0.1±0.06 -- 0.05±0.01 0.06±0.01 -- SFI 1H 0.08±0.06 -- 0.05±0.01 0.05±0.01 --

Mean± Standard Deviation 0.09±0.03 -- 0.05±0.02 0.05±0.02 0.03±0.07

MDL 0.05 0.05 0.042 0.035 0.072

Aluminum oxide ranges from 0 to 0.46 wt % and MgO ranges from 0 to 9 wt % (Figure

6.10). Combinations of oxides from Prieto were plotted and there is a lot of variation and

overlap with other quarries (Figure 6.8). Halite crystals were also visible in several

samples.

Summary

In all quarries, the most prevalent trace oxides were Al2O3, MgO, CaO, K2O, and

Na2O. There was no obvious correlation between the presence and absence of oxides.

Initially Al2O3, MgO, and CaO were plotted for all the points above minimum detection

limits. There are general trends in the combination of Al2O3, MgO, and CaO, but there was a lot of overlap between quarries. Comparisons of other combinations of oxides

55 could not be plotted because no other combination existed where a sample consistently had points with three oxides above detection limits.

Table 6.7 Average of points above EMPA minimum detection limits for nine samples from the quarry of Prieto.

Sample Oxide (wt %)

Al2O3 MgO CaO K2O Na2O

PRI 25 0.09±0.03 1.3±1.32 1.8±2.22 0.06±0.02 -- PRI 12 0.14±0.06 1.8±1.88 3.2±3.61 0.07±0.03 -- PRI 16 0.08±0.03 0.09±0.03 0.1±0.07 0.06±0.01 -- PRI 14 0.06 0.07±0.01 0.09±0.08 0.04±0.01 -- PRI 18 0.12±0.07 0.9±1.18 1.5±2.11 0.09±0.04 -- PRI 49 0.05±0.01 0.08±0.04 0.11±0.16 0.07±0.02 -- PRI 9 0.11±0.06 4.8±1.53 2.4±4.21 0.08±0.04 -- PRI 3 0.08±0.02 -- 0.06±0.01 0.06±0.02 --

Mean± Standard Deviation 0.09±0.03 1.1±1.6 1.1±1.2 0.07±0.02 --

MDL 0.05 0.05 0.042 0.035 0.072

56 8

4 MgO (wt %) 2

0 0 0.25 0.5

Al2O3 (wt %) Figure 6.10 Aluminum and magnesium oxide content from seven

samples representing the quarry of Prieto.

Stable Isotopes

Yolomecatl

Five representative chert samples from Yolomecatl were analyzed for δ18O and

δD values. The average δ18O value was 21.7‰ and δD -115.4‰ (VSMOW) (Table 6.8).

The δ18O values range from 21.3- 22.0‰ (VSMOW). δ-values cluster tightly near the

chert line of formation at 25ºC (Figure 6.11). Yolomecatl samples have the lightest δ18O

values. Host carbonate rocks from the quarry of Yolomecatl also have the lightest δ18O

values ranging from 20.5- 22.2‰ (VSMOW).

Chilapa

Five representative chert samples from Chilapa were analyzed for δ18O and δD

values. The average δ18O value is 25.0‰ and δD -110.8‰ (VSMOW) (Table 6.8). The

δ18O values range from 22.4- 28.2‰ (VSMOW). δ-values trend sub-parallel to chert formation at 25ºC (Figure 6.11).

57 Table 6.8 Isotopic composition (‰) of chert samples from all quarries.

Sample δ18O (VSMOW) δD (VSMOW)

YOLO 6 22.0 -117.6 YOLO 12 22.0 -116.4 YOLO 20 21.7 -114.6 YOLO 34 21.3 -115.6 YOLO 44 21.6 -112.8

Mean± Standard Deviation 21.7±0.3 -115.4±2

CHI 67 24.7 -108.6 CHI 84 22.4 -121.9 CHI 23 28.2 -95.3 CHI 12 26.8 -119.5 CHI 35 22.8 -108.5

AVE 25.0±2 -110.8±10

SFI 1H 21.6 -109.6 SFI 1E 22.0 -117.2 SFI FA 22.0 -112.9 SFI FB 22.0 -114.7 SFI 1D 22.0 -115.8

Mean± Standard Deviation 21.9±0.2 -114.0±3

PRI 49 24.3 -122.9 PRI 22 23.6 -116.6 PRI 83 23.6 -121.5 PRI 17 27.4 -59.9 PRI 9 25.4 -113.1

Mean± Standard Deviation 24.9±2 -106.8±27

58 250

200 Yolomecatl 150 Chilapa San Felipe Ixtapa 100 Prieto Series5 50 Series6 Meteoric Water

0 D (SMOW)

δ -50

-100

-150

-200

-250 20 22 24 26 28 30 δ18Ο (SMOW)

Figure 6.11 δ18O and δD values of silicates of all quarries. Formation waters are depleted in oxygen and D-enriched. Dotted line represents meteoric water.

San Felipe Ixtapa

Five representative chert samples from San Felipe Ixtapa were analyzed for δ18O and δD values. The average δ18O value is 21.9‰ and δD -114.0‰ (VSMOW) (Table

6.8). The δ18O values range from 21.6- 22.0‰ (VSMOW). δ-values cluster tightly near the chert line of formation at 25ºC and overlap Yolomecatl samples (Figure 6.11). San

Felipe Ixtapa samples have relatively light δ18O values.

Prieto

Five representative chert samples from Prieto were analyzed for δ18O and δD

values. The average δ18O value is 24.9‰ and δD -106.8‰ (VSMOW) (Table 6.8). The

59 δ18O values range from 23.6- 27.4‰ (VSMOW). δ-values sub-parallel to formation at

25ºC (Figure 6.11).

Summary

Two quarries, Yolomecatl and San Felipe Ixtapa both have similar 18O and

deuterium values with little deviation. The quarries of Chilapa and Prieto have similar values with considerable deviation in deuterium (Table 6.6). Knauth and Epstein (1976) found cherts to be 18O- enriched but depleted in deuterium relative to the waters in which

they formed. Hypothetical waters chert would have formed in equilibrium with were

calculated and plot along the meteoric water line for Yolomecatl and San Felipe Ixtapa

samples, but there is spread in the 18O values deviating from meteoric water for the quarries of Chilapa and Prieto (Figure 6.11). Chert from the quarries of Yolomecatl and

San Felipe Ixtapa was extracted from a diagenetically altered carbonate host rock the

Teposcolula Formation. Chert from both the quarries of Chilapa and Prieto were also

extracted from the Chilapa Formation which likely contributed to the similarity of isotope

values.

CHAPTER SEVEN

DISCUSSION & CONCLUSIONS

The initial objectives of this project were to examine chemical and compositional differences in naturally occurring chert formations in Oaxaca using a detailed geological and geochemical study of four separate quarries. Specific physical attributes contributed to the desirability of a quarry in stone tool production and trade. The goal of this project was to identify compositional differences that contributed to the desirability of a chert source for stone tool production in ancient Oaxaca. Based on the results of the analytical methods- XRD, HF treatment, EMPA, and stable isotope analysis- the following observations about Oaxacan cherts sampled in this study can be made.

Physical Properties and Petrography

Both Yolomecatl and San Felipe Ixtapa samples were similar in color and luster.

Both quarries were located NW of Pueblo Viejo approximately 5 km apart where archaeologists speculate chert tools moved into the Teposcolula Valley (personal communication S. Kowalewski). Chert samples at both quarries were extracted from the

Teposcolula Formation of recrystallized Cretaceous carbonate rock. Extracting pieces of chert large enough for tool production was difficult and samples were often highly fractured. It is possible other outcrops of chert from the Teposcolula Fm. are of higher quality and may have entered the valley through trade with Tixa Viejo.

Samples from Chilapa and Prieto were similar in color spanning a broad range of brown hues. The quarry of Chilapa is located approximately 10 km NW of Pueblo Viejo while Prieto is 7-8 km east of the archaeological site. The quarry of Prieto demonstrated the strongest evidence of a working quarry. Cobbles of chert previously removed from

61 limestone and tested for tool production were collected at Prieto. Located on the ridge overlooking the Nochixtlan Valley, Prieto chert was likely traded with towns in this valley. At the quarry of Chilapa chert was easily extracted as nodules from the Chilapa

Fm. Evidence such as whole projectile points and debitage of chert was found at Chilapa.

In thin section, both Yolomecatl and San Felipe Ixtapa samples were primarily composed of microquartz with minor amounts of chalcedony. Yolomecatl lacked evidence of fossils while San Felipe Ixtapa had several well-preserved silicified gastropods. During chert formation at San Felipe Ixtapa compaction was negligible based on the preserved fossil structure. However, at Yolomecatl compaction of clay material during chert formation is evident in thin section.

Thin section samples from Chilapa and Prieto were quite different in clay content despite the similarities in hand sample. Chilapa samples were primarily composed of microquartz with the exception of one sample that was estimated to be approximately 70 percent chalcedony. The dominant quartz phase in samples from Prieto was microquartz, however all samples had large amounts of clay present; upwards of 50 percent.

Additionally, Prieto samples had large caches of bivalves Tertiary in age. Prieto samples were likely formed in the Chilapa Fm. based on thin section comparison with samples collected at Chilapa.

Physical characteristics of chert from Yolomecatl and San Felipe Ixtapa were very similar, the slight discrepancies recognized in thin section are attributed here to geographical variation. The vast differences between the Yolomecatl and San Felipe

(Teposcolula Fm.) samples versus those of Chilapa and Prieto (Chilapa Fm.) are clearly a result of stratigraphic formation variation and diagenetic processes. The presence of

62 bivalves in Prieto samples, but lack of fossils in Chilapa chert could be due to

stratigraphic variation within the Chilapa Fm. or preferential clustering of organisms

within a depositional environment.

Hydrofluoric Acid Treatment

Hydrofluoric acid treatment also supported the dominant quartz phase to be

microquartz for both Yolomecatl and San Felipe Ixtapa. Samples from both quarries also

had traces of iron-bearing sediments or fluids during initial silicification. Based on color and streak iron-rich minerals are interpreted as hematite. Yolomecalt samples had a few well-preserved ostracod samples. It is possible the fossils interpreted as bivalves in thin

section could also be ostracods.

Samples treated with hydrofluoric acid from Chilapa were dominated by

microquartz, but several samples had vugs filled with microquartz. Residual organic

material resulting from clay components in Prieto samples was visible with HF treatment.

Prieto samples also had large caches of ostracods. The initial objective in using HF

treatment was used to isolate sponge spicules and radiolarian (Pessagno and Newport,

1972). The lack of silica producing sponges and radiolarian indicates the formation of

chert had to be under near-shore conditions likely in a mixing zone where meteoric water

provided silica in solution.

Electron Microprobe Analysis

The magnesium content of Yolomeacatl and Chilapa is not a representative characteristic of these quarries because two of nine and one of eight samples respectively had detectable amounts of magnesium. San Felipe Ixtapa did not have any detectable

amounts of magnesium. Prieto had the most samples containing detectable amounts of

63 magnesium. Although the average amount of magnesium was 1.1±1.6 wt %, a high

degree of error was associated with oxides from Prieto samples. However, halite crystals were visible in Prieto samples suggesting evaporite conditions during quartz

precipitation.

Yolomecatl and San Felipe Ixtapa had minor amounts of clay visible in thin

section. However EMPA was incapable of defining the trapped clay components in

significant concentrations to differentiate between quarries or make correlations between

the presence of different oxides. If the standard deviation for each point was plotted as

the error the fields of each quarry would completely overlap and not be capable of

distinguishing an individual quarry.

Stable Isotopes

Based on quartz-water oxygen isotope fractionation (1000 ln α = 3.09 x 106 T-2 –

3.29) temperatures of chert crystallization for Yolomecatl and San Felipe Ixtapa range between 34-25ºC (Knauth and Epstein, 1976). These temperatures are inconsistent with previous research by Knauth and Epstein (1976) who ascertain Cretaceous chert formation temperatures to be 10ºC lower. Also, Gao and Land (1991) suggest marine chert forming at near surface conditions between 35-25ºC to have δ18O values from +28.6

to +30.9‰. Depleted δ18O values are interpreted to form or be altered by 18O-depleted

meteoric water or hot water (Gao and Land, 1991). Previous research asserts the

temperatures of Post-Jurassic chert crystallization to range between 25-17ºC (Knauth and

Epstein, 1976). Samples from both Chilapa and Prieto are consistent with temperatures of

Post-Jurassic chert crystallization. Chert from the quarries of Yolomecatl and San Felipe

Ixtapa formed under elevated temperatures associated with magmatism during the

64 Cretaceous. Metamorphic fluids increased meteoric water temperatures during the subduction of ocean crust and collision of the Mixteco and Zapoteco terranes in the

Cretaceous. Chert from the quarries of Chilapa and Prieto formed under erratic temperatures associated with near-shore mixing zone variability.

Conclusions

Based on observations physical attributes were found that distinguished chert from Cretaceous versus Tertiary rocks. Unfortunately the methods used had mixed or limited success in identifying chemical or compositional differences unique to a specific quarry. In the field it was obvious that chert from the quarry of Prieto had been tested for stone tool production. There were also small isolated working pits at Yolomecatl. Chert from Prieto and Yolomecatl could have entered the Teposcolula Valley by way of trade networks with the Nochixtlan Valley and Tixa Viejo respectively. Although the presence and abundance of ostracod fossils in samples from Prieto do distinguish the quarry from

Yolomecatl, San Felipe Ixtapa, and Chilapa, the unpredictability of fossil deposits question the accuracy in representing the entire quarry.

Finally, the evaluation of my original research hypothesis that significant compositional differences exist between the chert examined in this study cannot be affirmed. Although the techniques and methods used in this study did bring to light interesting information regarding the formation of chert, more research is required to definitively answer questions regarding the quality and desirability of a chert resource.

Suggestions for future work include:

1. Surface exposure of both the Cretaceous Teposcolula Fm. and the Tertiary

Chilapa Fm. is extensive throughout the Teposcolula Valley. A more detailed

65 field study of potential working quarries is necessary to identify all possible chert

sources for stone tool production.

2. Completely dissolving quartz from a large sample may isolate clay and organic

material. A larger sample of clay components and a more refined technique such

as inductively couple mass spectrometry may be capable of identifying discrete

clay components that contribute to a source’s quality.

3. A more comprehensive analysis of preserved fossils to distinguish between

bivalves and ostradcods might be characteristic of a quarry. Additional potential

stratigraphic variation should also be assessed.

4. A systematic study by X-Ray and petrography of SiO2 forms might be useful.

Preliminary results presented have shown differences.

5. A detailed study of fossils in the Cretaceous chert versus the Tertiary chert and

the abundance might be a defining characteristic of chert from different ages of

deposits.

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80 Appendix A. All chert samples and the various methods used in this study.

Yolomecatl Thin Sample Section HF XRD EMPA Isotopes YOLO 4 x YOLO 6 x x x x YOLO 9 x YOLO 11 x YOLO 12 x x x x YOLO 16 x YOLO 17 x YOLO 18 x YOLO 19 x YOLO 20 x x x x YOLO 22 x YOLO 23 x YOLO 24 x YOLO 25 x YOLO 31 x YOLO 32 x YOLO 34 x x x x YOLO 37 x YOLO 38 x YOLO 39 x YOLO 41 x YOLO 43 x YOLO 44 x x x x YOLO 46 x YOLO 47 x YOLO 48 x

81 Chilapa Thin Sample Section HF XRD EMPA Isotopes CHI 7 x CHI 12 x x x CHI 22 x CHI 23 x x x CHI 26 x CHI 34 x CHI 35 x x x CHI 36 x CHI 39 x CHI 44 x CHI 56 x CHI 62 x CHI 63 x CHI 64 x CHI 67 x x x CHI 68 x CHI 73 x CHI 80 x CHI 81 x CHI 84 x x CHI 97 x CHI 99 x CHI 103 x CHI 104 x CHI 111 x

San Felipe Ixtapa Thin Sample Section HF XRD EMPA Isotopes SFI FA x x x x SFI FB x x x x x SFI FC.3 x SFI 1A x x SFI 1B x SFI 1B.2 x SFI 1C x x SFI 1D x x x SFI 1E x x x SFI 1G x SFI 1H x x x SFI 1H.2 x SFI 1J.3 x SFI 1K.4 x x SFI 1K.5 x

82 Prieto Thin Sample Section HF XRD EMPA Isotopes PRI CH 01 x PRI CH 03 x PRI CH 8 x PRI CH 09 x x x x PRI CH 12 x PRI CH 14 x PRI CH 15 x PRI CH 16 x PRI CH 17 x x x x PRI CH 18 x PRI CH 22 x x x x PRI CH 24 x PRI CH 25 x PRI CH 29 x PRI CH 32 x PRI CH 38 x PRI CH 42 x PRI CH 49 x x x x PRI CH 51 x PRI CH 53 x PRI CH 55 x PRI CH 72 x PRI CH 83 x x x x PRI CH 84 x

83 Appendix B. Peak positions in degrees and d-spacing and relative intensity of XRD samples.

Yolo-20 Random Powder Mount Yolo-34 Random Powder Mount

Position Rel. Int. Position Rel. Int. (Deg.) (DSp.) (Deg.) (Deg.) (DSp.) (Deg.) 5.31 19.31 29.98 12.68 8.10 14.37 12.70 8.09 9.32 24.27 4.25 362.45 21.42 4.81 0.14 29.80 3.48 21.48 22.63 4.56 2.95 31.05 3.34 2452.81 24.29 4.25 330.78 41.09 2.55 29.34 24.65 4.19 105.11 42.73 2.46 82.27 31.07 3.34 2351.89 44.21 2.38 13.29 34.38 3.03 38.61 46.20 2.28 146.05 41.10 2.55 20.06 47.15 2.24 33.96 42.75 2.45 74.80 49.72 2.13 81.18 44.21 2.38 14.57 50.81 2.08 20.63 46.22 2.28 145.56 53.71 1.98 41.30 47.16 2.24 24.47 58.95 1.82 193.14 49.74 2.13 63.86 64.70 1.67 39.34 50.80 2.09 21.89 65.23 1.66 18.16 53.73 1.98 37.42 67.93 1.60 26.42 58.96 1.82 177.96 61.99 1.74 10.21 64.72 1.67 36.03 65.29 1.66 15.17 67.96 1.60 13.16

CHI-12 Random Powder Mount CHI-84 Random Powder Mount

Position Rel. Int. Position Rel. Int. (Deg.) (DSp.) (Deg.) (Deg.) (DSp.) (Deg.) 31.04 3.34 100.00 12.69 8.09 0.32 24.26 4.26 14.48 18.27 5.63 0.13 58.92 1.82 7.21 21.67 4.76 0.10 46.19 2.28 5.57 24.27 4.26 16.19 42.71 2.46 3.28 29.84 3.47 0.39 49.70 2.13 2.67 31.05 3.34 100.00 41.05 2.55 1.57 36.12 2.89 0.27 53.69 1.98 1.51 41.08 2.55 1.46 64.68 1.67 1.48 42.73 2.46 3.97 47.15 2.24 1.25 44.17 2.38 0.84 50.80 2.09 1.06 46.20 2.28 5.48 67.91 1.60 0.72 47.16 2.24 1.57 65.20 1.66 0.68 49.72 2.13 2.88 23.24 4.44 0.64 50.79 2.09 0.79 61.88 1.74 0.46 53.71 1.98 2.00 12.68 8.10 0.44 58.95 1.82 8.82 44.19 2.38 0.28 61.90 1.74 0.15 64.72 1.67 1.57 67.93 1.60 0.44

85 SFI FA Random Powder SFI FB Random Powder

Position Rel. Int. Position Rel. Int. (Deg.) (DSp.) (Deg.) (Deg.) (DSp.) (Deg.) 12.67 8.11 0.37 12.72 8.07 0.60 17.79 5.79 0.97 24.25 4.26 14.47 21.47 4.80 0.15 25.23 4.10 2.63 24.24 4.26 27.90 29.80 3.48 2.29 25.43 4.06 0.37 31.03 3.34 100.00 29.83 3.47 0.59 41.08 2.55 0.96 31.04 3.34 100.00 41.85 2.50 0.54 41.09 2.55 1.11 42.09 2.49 0.23 42.73 2.46 3.03 42.71 2.46 3.14 44.18 2.38 0.60 44.22 2.38 0.25 46.19 2.28 5.07 46.18 2.28 6.20 47.12 2.24 1.03 47.13 2.24 1.05 49.71 2.13 2.58 49.69 2.13 2.94 50.80 2.09 1.09 50.77 2.09 1.22 53.66 1.98 1.35 53.68 1.98 1.24 58.93 1.82 7.32 58.92 1.82 7.89 61.87 1.74 0.46 64.71 1.67 1.47 61.95 1.74 0.54 67.95 1.60 0.95 62.06 1.74 0.63 67.95 1.60 0.95 64.70 1.67 1.49 65.24 1.66 0.65 67.92 1.60 0.54

PRI-22 Random Powder PRI-83 Random Powder Mount

Position Rel. Int. Position Rel. Int. (Deg.) (DSp.) (Deg.) (Deg.) (DSp.) (Deg.) 12.66 8.11 1.31 12.36 8.31 0.32 24.27 4.26 14.39 24.25 4.26 15.40 31.04 3.34 100.00 29.80 3.48 0.76 35.96 2.90 1.59 31.02 3.35 100.00 41.07 2.55 1.18 41.07 2.55 1.19 42.71 2.46 3.39 42.69 2.46 3.79 44.22 2.38 0.33 46.17 2.28 5.30 46.19 2.28 5.31 47.12 2.24 1.34 47.15 2.24 1.36 49.68 2.13 2.89 48.04 2.20 0.13 50.81 2.09 1.10 49.70 2.13 2.63 53.69 1.98 1.56 50.80 2.09 0.65 58.91 1.82 8.04 53.71 1.98 1.69 61.93 1.74 0.35 58.94 1.82 8.02 64.67 1.67 1.57 61.90 1.74 0.19 67.93 1.60 0.56 64.70 1.67 1.38 67.92 1.60 0.43

86 Appendix C. EMP results for all four quarries. Thirty points were measured per sample.

YOLO-CH-24 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 97.08 0.61 0.01 0.03 0.06 0.17 0.11 0.06 2 94.31 1.59 0.07 0.03 0.00 0.48 0.32 0.12 3 94.98 0.71 0.05 0.05 0.00 0.18 0.09 0.09 4 95.69 1.01 0.05 0.01 0.00 0.32 0.16 0.05 5 91.33 1.44 0.10 0.11 0.00 0.45 0.17 0.08 6 92.90 0.81 0.05 0.10 0.06 0.38 0.13 0.08 7 97.62 0.20 0.00 0.00 0.00 0.06 0.09 0.07 8 96.90 0.32 0.01 0.00 0.12 0.17 0.12 0.05 9 92.49 1.40 0.11 0.08 0.04 0.52 0.20 0.07 10 98.01 0.22 0.00 0.00 0.02 0.04 0.09 0.04 11 98.46 0.13 0.01 0.00 0.00 0.03 0.05 0.03 12 97.78 0.19 0.01 0.06 0.08 0.07 0.05 0.05 13 94.43 0.08 0.02 0.00 0.00 0.05 0.00 0.02 14 96.55 0.40 0.02 0.00 0.05 0.14 0.13 0.09 15 95.97 0.43 0.00 0.00 0.06 0.12 0.09 0.07 16 94.39 1.06 0.03 0.00 0.00 0.42 0.16 0.09 17 93.05 0.74 0.03 0.04 0.00 0.27 0.09 0.10 18 94.37 0.79 0.03 0.08 0.00 0.38 0.12 0.08 19 93.19 1.34 0.08 0.04 0.06 0.47 0.17 0.14 20 95.24 0.77 0.03 0.08 0.00 0.28 0.11 0.06 21 91.12 0.66 0.01 0.07 0.00 0.30 0.10 0.06 22 88.31 1.16 0.07 0.14 0.09 0.49 0.16 0.07 23 94.17 1.11 0.04 0.13 0.00 0.41 0.16 0.10 24 94.35 0.56 0.03 0.07 0.00 0.14 0.10 0.05 25 92.58 1.00 0.06 0.04 0.00 0.37 0.15 0.08 26 97.65 0.49 0.02 0.07 0.00 0.13 0.11 0.04 27 93.76 0.97 0.03 0.04 0.06 0.38 0.14 0.06 28 92.58 0.55 0.01 0.04 0.00 0.17 0.08 0.06 29 92.37 1.27 0.10 0.13 0.00 0.37 0.18 0.05 30 94.28 0.79 0.02 0.00 0.00 0.30 0.18 0.03

MDL 0.05 0.05 0.05 0.15 0.14 0.04 0.04 0.07

Mean 0.76 0.07 0.27 0.13 0.07 Variance 0.18 0.00 0.02 0.00 0.00 Standard Deviation 0.42 0.02 0.15 0.06 0.03

87 YOLO- CH-6 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.83 0.06 0.00 0.00 0.00 0.02 0.03 0.00 2 102.21 0.05 0.00 0.04 0.01 0.09 0.04 0.01 3 99.57 0.04 0.02 0.00 0.00 0.04 0.01 0.00 4 99.46 0.01 0.00 0.00 0.01 0.03 0.00 0.01 5 99.40 0.01 0.02 0.00 0.02 0.30 0.00 0.00 6 98.97 0.01 0.02 0.00 0.09 0.39 0.03 0.01 7 92.75 0.03 0.06 0.00 0.02 1.71 0.02 0.02 8 99.48 0.12 0.01 0.02 0.06 0.11 0.06 0.00 9 96.36 0.01 0.00 0.05 0.00 0.05 0.15 0.31 10 97.80 0.03 0.01 0.00 0.00 0.19 0.03 0.00 11 95.46 0.00 0.00 0.01 0.01 0.05 0.02 0.02 12 99.77 0.03 0.01 0.00 0.00 0.03 0.01 0.00 13 99.06 0.03 0.02 0.00 0.04 0.26 0.03 0.00 14 99.22 0.12 0.01 0.00 0.02 0.07 0.07 0.00 15 99.69 0.07 0.03 0.03 0.04 0.23 0.03 0.05 16 98.35 0.11 0.00 0.00 0.02 0.08 0.03 0.00 17 98.63 0.06 0.01 0.01 0.00 0.16 0.05 0.01 18 98.85 0.02 0.01 0.07 0.06 0.04 0.03 0.01 19 99.53 0.03 0.02 0.01 0.04 0.02 0.01 0.02 20 99.59 0.04 0.00 0.10 0.00 0.04 0.03 0.02 21 98.98 0.01 0.03 0.01 0.01 0.03 0.01 0.02 22 99.32 0.00 0.03 0.00 0.07 0.01 0.02 0.01 23 98.55 0.04 0.00 0.00 0.02 0.23 0.00 0.03 24 99.54 0.02 0.00 0.05 0.00 0.03 0.02 0.00 25 99.64 0.01 0.01 0.12 0.04 0.05 0.02 0.01 26 99.57 0.01 0.00 0.04 0.00 0.07 0.00 0.00 27 99.47 0.03 0.02 0.00 0.05 0.07 0.01 0.03 28 99.03 0.00 0.00 0.01 0.00 0.03 0.00 0.00 29 98.82 0.09 0.02 0.00 0.06 0.05 0.03 0.01 30 90.81 0.05 0.05 0.00 0.00 4.41 0.04 0.01

MDL 0.05 0.05 0.05 0.15 0.14 0.04 0.04 0.07

Mean 0.08 0.05 0.43 0.07 0.00 Variance 0.00 0.00 1.01 0.00 Standard Deviation 0.03 0.00 1.01 0.04

88 YOLO-CH-20 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 99.44 0.02 0.00 0.00 0.05 0.03 0.00 0.01 2 99.61 0.04 0.00 0.00 0.01 0.03 0.01 0.02 3 98.45 0.09 0.01 0.00 0.00 0.04 0.03 0.01 4 99.58 0.01 0.00 0.03 0.04 0.04 0.01 0.01 5 97.49 0.02 0.01 0.04 0.06 0.05 0.01 0.02 6 99.31 0.15 0.02 0.01 0.00 0.05 0.06 0.01 7 98.09 0.11 0.00 0.01 0.00 0.01 0.01 0.01 8 97.24 0.00 0.02 0.05 0.00 0.03 0.01 0.00 9 96.39 0.04 0.01 0.01 0.00 0.05 0.01 0.03 10 97.33 0.00 0.00 0.05 0.06 0.04 0.02 0.00 11 99.08 0.01 0.00 0.01 0.00 0.05 0.02 0.02 12 99.33 0.04 0.01 0.01 0.00 0.02 0.03 0.01 13 99.84 0.03 0.00 0.01 0.06 0.01 0.01 0.03 14 99.78 0.02 0.00 0.00 0.00 0.03 0.01 0.00 15 96.24 0.07 0.01 0.00 0.06 0.04 0.00 0.04 16 98.92 0.03 0.02 0.01 0.00 0.01 0.01 0.02 17 98.28 0.03 0.00 0.07 0.00 0.07 0.02 0.01 18 98.48 0.02 0.02 0.01 0.00 0.10 0.00 0.00 19 98.90 0.09 0.02 0.00 0.00 0.03 0.01 0.00 20 98.31 0.04 0.00 0.07 0.09 0.02 0.00 0.00 21 98.87 0.00 0.00 0.00 0.04 0.05 0.00 0.03 22 99.00 0.05 0.02 0.00 0.01 0.03 0.00 0.00 23 99.59 0.00 0.00 0.00 0.00 0.00 0.01 0.00 24 98.23 0.06 0.00 0.00 0.00 0.04 0.04 0.00 25 99.61 0.03 0.00 0.06 0.00 0.01 0.00 0.00 26 98.78 0.02 0.00 0.08 0.01 0.03 0.03 0.03 27 98.52 0.11 0.00 0.01 0.00 0.04 0.02 0.03 28 99.62 0.00 0.00 0.07 0.01 0.01 0.00 0.01 29 99.46 0.04 0.00 0.00 0.00 0.01 0.01 0.00 30 99.33 0.05 0.00 0.03 0.00 0.08 0.03 0.00

MDL 0.05 0.05 0.05 0.15 0.14 0.04 0.04 0.07

Mean 0.09 0.00 0.06 0.00 0.00 Variance 0.00 0.00 Standard Deviation 0.03 0.02

89 YOLO-CH-12 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.18 0.06 0.04 0.00 0.02 0.03 0.03 0.00 2 97.78 0.07 0.01 0.01 0.11 0.03 0.02 0.00 3 96.78 0.11 0.00 0.00 0.06 0.03 0.01 0.00 4 99.31 0.15 0.00 0.00 0.00 0.05 0.07 0.00 5 97.03 0.05 0.00 0.03 0.03 0.01 0.03 0.01 6 96.77 0.03 0.00 0.01 0.01 0.00 0.01 0.03 7 98.66 0.00 0.00 0.00 0.00 0.00 0.02 0.02 8 99.52 0.00 0.00 0.00 0.00 0.06 0.02 0.00 9 97.99 0.08 0.00 0.01 0.05 0.12 0.05 0.00 10 96.11 0.08 0.01 0.00 0.00 0.01 0.03 0.00 11 99.70 0.00 0.00 0.05 0.00 0.00 0.02 0.00 12 99.13 0.10 0.00 0.00 0.04 0.07 0.03 0.00 13 100.71 0.04 0.00 0.09 0.00 0.01 0.00 0.01 14 99.60 0.00 0.00 0.01 0.00 0.02 0.00 0.02 15 99.43 0.13 0.00 0.06 0.04 0.01 0.05 0.05 16 98.96 0.13 0.00 0.02 0.00 0.01 0.04 0.03 17 99.71 0.16 0.00 0.00 0.02 0.06 0.07 0.02 18 99.71 0.08 0.00 0.04 0.00 0.01 0.02 0.01 19 99.10 0.08 0.00 0.05 0.09 0.08 0.04 0.02 20 96.57 0.11 0.00 0.00 0.00 0.03 0.05 0.04 21 97.70 0.09 0.00 0.00 0.05 0.06 0.03 0.00 22 96.84 0.02 0.00 0.02 0.02 0.15 0.00 0.02 23 97.50 0.02 0.00 0.00 0.00 0.00 0.02 0.00 24 99.61 0.08 0.00 0.01 0.00 0.04 0.04 0.03 25 98.81 0.28 0.01 0.01 0.00 0.03 0.08 0.01 26 99.71 0.13 0.00 0.01 0.01 0.07 0.03 0.03 27 99.37 0.22 0.00 0.00 0.00 0.03 0.10 0.01 28 98.75 0.03 0.00 0.00 0.00 0.01 0.03 0.01 29 98.44 0.14 0.00 0.00 0.00 0.23 0.05 0.03 30 97.50 0.09 0.00 0.04 0.06 0.02 0.04 0.01

MDL 0.05 0.05 0.05 0.15 0.14 0.04 0.04 0.07

Mean 0.11 0.00 0.10 0.06 0.00 Variance 0.00 0.00 0.00 Standard Deviation 0.05 0.06 0.02

90 YOLO-CH-43 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 101.27 0.01 0.02 0.00 0.00 0.01 0.00 0.00 2 98.00 0.01 0.02 0.00 0.00 0.00 0.00 0.02 3 98.29 0.06 0.00 0.00 0.00 0.04 0.03 0.00 4 97.32 0.01 0.01 0.00 0.04 0.00 0.00 0.03 5 98.06 0.05 0.01 0.00 0.00 0.04 0.01 0.01 6 98.62 0.00 0.00 0.00 0.00 0.02 0.00 0.00 7 97.78 0.02 0.00 0.00 0.04 0.01 0.01 0.00 8 98.64 0.02 0.00 0.00 0.00 0.03 0.02 0.04 9 98.66 0.00 0.00 0.00 0.00 0.02 0.02 0.02 10 97.91 0.02 0.00 0.00 0.00 0.01 0.00 0.02 11 97.67 0.00 0.00 0.00 0.00 0.03 0.01 0.01 12 97.19 0.02 0.01 0.00 0.00 0.02 0.01 0.00 13 98.02 0.05 0.01 0.02 0.00 0.03 0.01 0.02 14 97.68 0.08 0.03 0.03 0.00 0.10 0.03 0.01 15 98.60 0.01 0.00 0.07 0.02 0.03 0.01 0.01 16 98.27 0.04 0.00 0.00 0.00 0.02 0.01 0.00 17 98.21 0.00 0.01 0.01 0.01 0.11 0.00 0.00 18 98.70 0.02 0.02 0.01 0.07 0.03 0.02 0.01 19 98.00 0.06 0.01 0.02 0.00 0.07 0.02 0.00 20 98.42 0.03 0.00 0.00 0.02 0.04 0.00 0.02 21 98.11 0.15 0.01 0.00 0.02 0.05 0.05 0.01 22 98.09 0.01 0.01 0.02 0.00 0.02 0.02 0.00 23 97.77 0.00 0.00 0.10 0.00 0.09 0.02 0.01 24 98.52 0.06 0.00 0.00 0.00 0.05 0.01 0.01 25 97.93 0.06 0.00 0.04 0.00 0.02 0.01 0.00 26 97.84 0.03 0.01 0.04 0.00 0.02 0.02 0.01 27 98.83 0.02 0.02 0.01 0.00 0.03 0.00 0.01 28 97.21 0.05 0.02 0.00 0.00 0.05 0.02 0.02 29 97.69 0.00 0.00 0.00 0.02 0.01 0.00 0.00 30 97.91 0.00 0.00 0.04 0.00 0.05 0.00 0.00 25 97.51 0.03 0.00 0.04 0.05 0.05 0.01 0.05

MDL 0.05 0.05 0.05 0.18 0.14 0.04 0.03 0.07

Mean 0.07 0.00 0.06 0.00 0.00 Variance 0.00 0.00 Standard Deviation 0.03 0.02

91 YOLO- CH-9 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 97.36 0.16 0.00 0.01 0.00 0.03 0.07 0.03 2 98.59 0.11 0.00 0.01 0.01 0.15 0.05 0.01 3 98.06 0.15 0.01 0.00 0.00 0.10 0.07 0.01 4 97.31 0.09 0.00 0.01 0.04 0.05 0.04 0.03 5 98.65 0.07 0.00 0.02 0.04 0.02 0.04 0.00 6 97.64 0.24 0.02 0.09 0.00 0.05 0.11 0.05 7 98.13 0.08 0.01 0.01 0.00 0.04 0.03 0.00 8 97.54 0.27 0.00 0.03 0.05 0.04 0.09 0.03 9 97.83 0.09 0.00 0.02 0.00 0.22 0.01 0.03 10 98.27 0.04 0.02 0.09 0.03 0.03 0.04 0.00 11 98.17 0.10 0.00 0.08 0.06 0.03 0.04 0.02 12 98.62 0.05 0.03 0.00 0.03 0.05 0.01 0.02 13 98.43 0.09 0.00 0.00 0.03 0.04 0.06 0.02 14 99.14 0.16 0.02 0.00 0.01 0.05 0.05 0.02 15 98.00 0.19 0.03 0.00 0.00 0.04 0.06 0.05 16 97.67 0.08 0.01 0.04 0.00 0.02 0.03 0.01 17 98.59 0.06 0.00 0.01 0.00 0.02 0.02 0.00 18 96.67 0.15 0.02 0.04 0.00 0.02 0.04 0.00 19 97.04 0.12 0.00 0.07 0.05 0.08 0.03 0.04 20 99.21 0.06 0.00 0.00 0.00 0.02 0.04 0.02 21 96.29 0.10 0.02 0.10 0.01 0.02 0.03 0.00 22 97.59 0.22 0.03 0.03 0.00 0.02 0.07 0.01 23 95.98 0.18 0.00 0.08 0.00 0.08 0.07 0.05 24 96.91 0.17 0.00 0.00 0.00 0.06 0.06 0.01 25 99.17 0.17 0.00 0.00 0.00 0.02 0.08 0.04 26 96.37 0.23 0.01 0.00 0.00 0.08 0.09 0.03 27 98.56 0.08 0.00 0.00 0.03 0.05 0.02 0.03 28 98.89 0.11 0.00 0.04 0.07 0.04 0.05 0.01 29 96.94 0.08 0.00 0.03 0.03 0.03 0.04 0.00 30 96.80 0.12 0.00 0.06 0.04 0.02 0.06 0.04

MDL 0.05 0.05 0.05 0.18 0.14 0.04 0.03 0.07

Mean 0.13 0.00 0.08 0.06 0.00 Variance 0.00 0.00 0.00 Standard Deviation 0.06 0.05 0.02

YOLO-CH-11 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.73 0.03 0.02 0.11 0.05 0.02 0.00 0.01 2 98.58 0.05 0.00 0.06 0.00 0.00 0.00 0.00 3 99.12 0.04 0.00 0.00 0.07 0.00 0.02 0.01 4 99.15 0.01 0.00 0.08 0.02 0.03 0.00 0.04 5 98.88 0.07 0.01 0.00 0.01 0.00 0.02 0.02 6 98.36 0.05 0.00 0.05 0.00 0.02 0.00 0.02 7 97.26 0.03 0.00 0.00 0.00 0.03 0.00 0.00 8 97.91 0.07 0.02 0.05 0.00 0.11 0.03 0.00 9 97.91 0.05 0.01 0.12 0.02 0.04 0.05 0.01 10 95.96 0.21 0.00 0.00 0.02 0.18 0.08 0.03 11 98.22 0.00 0.01 0.07 0.03 0.02 0.02 0.01 12 97.53 0.03 0.00 0.06 0.00 0.04 0.03 0.04 13 98.25 0.00 0.00 0.00 0.06 0.02 0.02 0.00 14 98.89 0.00 0.00 0.05 0.02 0.04 0.01 0.01 15 98.43 0.05 0.02 0.00 0.05 0.23 0.02 0.03 16 96.81 0.04 0.00 0.05 0.05 0.53 0.01 0.00 17 98.20 0.02 0.03 0.00 0.00 0.10 0.00 0.02 18 99.20 0.00 0.00 0.05 0.06 0.01 0.01 0.00 19 98.73 0.04 0.03 0.03 0.09 0.04 0.05 0.04 20 97.58 0.00 0.01 0.00 0.00 0.04 0.00 0.00 21 97.68 0.10 0.00 0.04 0.02 0.05 0.02 0.06 22 97.18 0.08 0.01 0.01 0.09 0.36 0.01 0.02 23 97.55 0.07 0.01 0.04 0.00 0.03 0.02 0.00 24 97.18 0.08 0.02 0.04 0.01 0.04 0.03 0.00 25 97.32 0.05 0.00 0.00 0.03 0.08 0.01 0.03 26 97.41 0.08 0.03 0.06 0.00 0.69 0.02 0.00 27 98.36 0.04 0.00 0.02 0.00 0.05 0.02 0.00 28 96.92 0.08 0.01 0.00 0.00 0.03 0.06 0.01 29 99.27 0.01 0.01 0.04 0.05 0.00 0.04 0.02 30 99.31 0.01 0.00 0.01 0.02 0.01 0.03 0.03

MDL 0.05 0.05 0.05 0.18 0.14 0.04 0.03 0.07

Mean 0.08 0.00 0.19 0.06 0.00 Variance 0.00 0.04 0.00 Standard Deviation 0.04 0.21 0.02

93 YOLO-CH-34 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 99.68 0.04 0.01 0.04 0.07 0.00 0.06 0.02 2 100.44 0.02 0.01 0.04 0.00 0.00 0.02 0.03 3 99.92 0.10 0.01 0.00 0.00 0.04 0.01 0.02 4 100.62 0.01 0.00 0.09 0.00 0.00 0.04 0.02 5 99.85 0.08 0.00 0.00 0.02 0.02 0.03 0.00 6 99.13 0.07 0.00 0.00 0.00 0.04 0.04 0.01 7 98.98 0.07 0.00 0.02 0.05 0.02 0.03 0.00 8 99.25 0.09 0.03 0.01 0.00 0.03 0.03 0.01 9 98.97 0.05 0.01 0.00 0.00 0.02 0.00 0.01 10 98.55 0.01 0.00 0.00 0.02 0.02 0.00 0.00 11 98.92 0.06 0.00 0.02 0.00 0.02 0.00 0.00 12 98.21 0.02 0.00 0.00 0.02 0.00 0.02 0.01 13 99.00 0.19 0.00 0.00 0.01 0.02 0.06 0.04 14 99.10 0.05 0.00 0.06 0.04 0.02 0.02 0.02 15 99.80 0.04 0.02 0.05 0.03 0.03 0.02 0.04 16 97.89 0.02 0.00 0.00 0.01 0.01 0.00 0.01 17 98.54 0.15 0.00 0.04 0.04 0.02 0.09 0.03 18 98.49 0.00 0.03 0.00 0.00 0.02 0.01 0.02 19 98.86 0.06 0.00 0.05 0.00 0.02 0.00 0.00 20 99.24 0.06 0.00 0.04 0.04 0.03 0.00 0.02 21 98.93 0.12 0.04 0.00 0.00 0.04 0.06 0.03 22 98.72 0.01 0.00 0.00 0.00 0.01 0.02 0.00 23 98.80 0.07 0.00 0.02 0.00 0.02 0.03 0.03 24 99.52 0.03 0.02 0.03 0.00 0.01 0.01 0.02 25 99.03 0.03 0.02 0.00 0.00 0.01 0.00 0.01 26 98.20 0.08 0.00 0.04 0.03 0.01 0.03 0.01 27 98.97 0.03 0.00 0.00 0.00 0.02 0.02 0.03 28 98.72 0.04 0.00 0.06 0.00 0.00 0.00 0.01 29 99.08 0.00 0.00 0.14 0.00 0.03 0.02 0.00 30 98.41 0.21 0.01 0.00 0.02 0.02 0.09 0.01 0.06 MDL 0.05 0.05 0.05 0.18 0.14 0.04 0.03 0.07

Mean 0.09 0.00 0.00 0.06 0.00 Variance 0.00 0.00 Standard Deviation 0.04 0.02

YOLO-CH-44 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.04 0.09 0.01 0.01 0.03 0.09 0.02 0.01 2 97.20 0.06 0.00 0.00 0.00 1.20 0.03 0.00 3 98.40 0.05 0.00 0.00 0.06 0.25 0.00 0.00 4 98.68 0.04 0.01 0.00 0.00 0.61 0.06 0.02 5 99.30 0.17 0.00 0.00 0.00 0.07 0.05 0.02 6 98.07 0.03 0.02 0.01 0.04 1.09 0.03 0.00 7 98.51 0.08 0.01 0.00 0.01 0.03 0.00 0.00 8 99.63 0.04 0.00 0.00 0.00 0.04 0.02 0.00 9 98.10 0.09 0.01 0.00 0.00 0.76 0.03 0.04 10 98.08 0.05 0.00 0.07 0.00 0.46 0.03 0.01 11 96.28 0.10 0.00 0.00 0.00 1.12 0.03 0.00 12 99.06 0.11 0.00 0.00 0.00 0.04 0.02 0.03 13 99.29 0.10 0.00 0.00 0.03 0.04 0.04 0.01 14 98.99 0.00 0.02 0.00 0.00 0.02 0.01 0.00 15 98.84 0.12 0.00 0.09 0.00 0.26 0.04 0.02 16 99.52 0.10 0.02 0.00 0.05 0.23 0.03 0.02 17 99.09 0.06 0.00 0.00 0.03 0.37 0.03 0.01 18 98.89 0.03 0.00 0.00 0.00 0.02 0.01 0.00 19 98.39 0.08 0.01 0.03 0.00 0.33 0.00 0.00 20 98.93 0.06 0.00 0.04 0.00 0.06 0.01 0.02 21 98.54 0.10 0.02 0.00 0.04 0.08 0.03 0.00 22 99.01 0.15 0.00 0.01 0.05 0.18 0.04 0.00 23 99.06 0.03 0.02 0.00 0.04 0.03 0.01 0.02 24 97.68 0.05 0.04 0.04 0.00 1.17 0.04 0.00 25 97.95 0.05 0.02 0.00 0.00 0.95 0.00 0.02 26 97.56 0.01 0.00 0.04 0.06 0.49 0.05 0.00 27 97.69 0.05 0.00 0.03 0.05 0.02 0.02 0.02 28 97.86 0.07 0.00 0.01 0.00 0.11 0.03 0.02 29 98.36 0.12 0.01 0.08 0.05 0.16 0.03 0.01 30 98.93 0.14 0.00 0.00 0.00 0.11 0.10 0.02

MDL 0.05 0.05 0.05 0.18 0.14 0.04 0.03 0.07

Mean 0.09 0.00 0.47 0.05 0.00 Variance 0.00 0.17 0.00 Standard Deviation 0.03 0.41 0.02

95 CHI-CH-104 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.58 0.03 0.00 0.00 0.00 0.01 0.03 0.03 2 98.75 0.07 0.03 0.00 0.08 0.07 0.01 0.00 3 99.17 0.05 0.03 0.00 0.06 0.02 0.00 0.00 4 98.53 0.11 0.05 0.00 0.02 0.05 0.04 0.01 5 97.97 0.05 0.00 0.02 0.00 0.01 0.04 0.05 6 99.14 0.02 0.00 0.13 0.08 0.07 0.00 0.00 7 98.34 0.02 0.00 0.03 0.06 0.02 0.03 0.04 8 98.68 0.19 0.04 0.00 0.06 0.05 0.03 0.05 9 99.06 0.03 0.00 0.06 0.07 0.03 0.01 0.03 10 98.49 0.07 0.01 0.00 0.01 0.03 0.02 0.01 11 99.27 0.08 0.01 0.02 0.00 0.07 0.02 0.04 12 98.78 0.08 0.02 0.03 0.03 0.01 0.04 0.02 13 98.65 0.07 0.02 0.12 0.04 0.02 0.03 0.03 14 98.72 0.09 0.00 0.02 0.07 0.07 0.03 0.02 15 99.90 0.09 0.02 0.11 0.00 0.06 0.00 0.04 16 98.75 0.01 0.03 0.00 0.00 0.03 0.01 0.00 17 98.53 0.05 0.00 0.02 0.04 0.02 0.03 0.02 18 96.82 0.04 0.02 0.00 0.00 0.00 0.03 0.04 19 97.25 0.00 0.00 0.07 0.00 0.01 0.02 0.04 20 95.17 0.05 0.00 0.11 0.01 0.04 0.02 0.05 21 92.29 0.04 0.01 0.02 0.00 0.03 0.02 0.03 22 88.31 0.02 0.02 0.00 0.00 0.02 0.03 0.03 23 97.69 0.02 0.01 0.01 0.00 0.04 0.02 0.03 24 98.67 0.02 0.00 0.02 0.09 0.01 0.01 0.02 25 99.01 0.06 0.00 0.08 0.02 0.01 0.02 0.03 26 98.72 0.04 0.01 0.04 0.00 0.04 0.02 0.02 27 99.00 0.04 0.02 0.02 0.00 0.02 0.02 0.03 28 98.45 0.08 0.03 0.00 0.00 0.05 0.00 0.05 29 98.80 0.04 0.03 0.00 0.00 0.00 0.06 0.02 30 98.77 0.05 0.03 0.01 0.08 0.04 0.05 0.03

MDL 0.05 0.05 0.05 0.16 0.15 0.04 0.03 0.07

Mean 0.08 0.00 0.06 0.04 0.00 Variance 0.00 0.00 0.00 Standard Deviation 0.03 0.01 0.01

96 CHI-CH-67 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.06 0.06 0.04 0.06 0.00 0.09 0.06 0.11 2 98.64 0.04 0.00 0.00 0.02 0.02 0.06 0.06 3 98.80 0.03 0.01 0.02 0.00 0.00 0.06 0.09 4 97.83 0.06 0.03 0.00 0.00 0.17 0.08 0.11 5 98.31 0.09 0.08 0.00 0.00 0.02 0.07 0.12 6 98.18 0.07 0.10 0.05 0.00 0.02 0.06 0.06 7 98.78 0.08 0.06 0.00 0.00 0.03 0.07 0.10 8 98.41 0.12 0.09 0.02 0.08 0.03 0.10 0.06 9 98.43 0.06 0.02 0.15 0.01 0.03 0.06 0.10 10 98.15 0.11 0.06 0.08 0.00 0.09 0.05 0.10 11 98.10 0.09 0.05 0.09 0.00 0.06 0.08 0.08 12 98.44 0.13 0.07 0.15 0.02 0.07 0.09 0.10 13 98.20 0.02 0.06 0.04 0.03 0.01 0.07 0.13 14 98.01 0.08 0.05 0.00 0.00 0.13 0.08 0.11 15 98.55 0.04 0.03 0.15 0.00 0.04 0.05 0.15 16 98.92 0.04 0.06 0.00 0.00 0.01 0.04 0.11 17 97.54 0.09 0.05 0.00 0.00 0.11 0.07 0.10 18 98.53 0.09 0.07 0.04 0.06 0.06 0.06 0.09 19 99.10 0.11 0.07 0.00 0.07 0.11 0.05 0.13 20 98.28 0.10 0.10 0.00 0.00 0.03 0.07 0.11 21 98.40 0.07 0.01 0.05 0.00 0.05 0.05 0.07 22 98.13 0.10 0.10 0.05 0.04 0.05 0.06 0.09 23 98.29 0.10 0.09 0.00 0.00 0.25 0.06 0.06 24 97.83 0.16 0.08 0.08 0.00 0.25 0.07 0.11 25 98.15 0.09 0.04 0.00 0.02 0.04 0.07 0.07 26 98.47 0.09 0.09 0.05 0.05 0.06 0.08 0.10 27 96.67 0.06 0.08 0.00 0.08 0.12 0.07 0.10 28 96.18 0.10 0.06 0.02 0.03 0.05 0.05 0.12 29 95.15 0.15 0.08 0.00 0.03 0.04 0.10 0.11 30 95.54 0.07 0.06 0.06 0.05 0.08 0.06 0.11

MDL 0.05 0.05 0.05 0.16 0.15 0.04 0.03 0.07

Mean 0.09 0.08 0.11 0.07 0.11 Variance 0.00 0.00 0.00 0.00 0.00 Standard Deviation 0.03 0.01 0.06 0.01 0.02

97 CHI-CH-26 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 96.56 0.02 0.02 0.02 0.03 0.02 0.04 0.02 2 97.41 0.00 0.00 0.00 0.03 0.03 0.01 0.01 3 97.77 0.00 0.02 0.00 0.03 0.05 0.04 0.12 4 98.50 0.01 0.02 0.00 0.00 0.04 0.00 0.00 5 98.34 0.12 0.03 0.00 0.02 0.05 0.03 0.01 6 98.60 0.00 0.00 0.00 0.00 0.01 0.00 0.00 7 98.48 0.01 0.03 0.02 0.00 0.03 0.01 0.02 8 98.59 0.02 0.00 0.09 0.01 0.03 0.02 0.00 9 99.07 0.06 0.01 0.00 0.00 0.02 0.03 0.01 10 98.50 0.10 0.00 0.07 0.02 0.05 0.02 0.03 11 99.38 0.04 0.00 0.00 0.00 0.01 0.03 0.01 12 99.11 0.03 0.02 0.02 0.00 0.07 0.02 0.02 13 98.77 0.04 0.01 0.03 0.00 0.03 0.01 0.01 14 98.65 0.03 0.00 0.00 0.02 0.01 0.02 0.06 15 99.08 0.00 0.01 0.02 0.05 0.01 0.01 0.00 16 98.81 0.02 0.02 0.00 0.05 0.04 0.07 0.09 17 99.33 0.04 0.03 0.00 0.00 0.02 0.00 0.03 18 99.19 0.02 0.00 0.15 0.00 0.03 0.03 0.02 19 98.75 0.04 0.00 0.00 0.09 0.01 0.03 0.01 20 99.25 0.01 0.01 0.00 0.00 0.04 0.00 0.02 21 98.55 0.06 0.02 0.00 0.01 0.04 0.02 0.01 22 99.00 0.01 0.02 0.05 0.00 0.04 0.03 0.03 23 98.62 0.02 0.00 0.03 0.00 0.04 0.01 0.01 24 98.84 0.04 0.01 0.02 0.00 0.05 0.00 0.00 25 99.15 0.07 0.00 0.06 0.00 0.03 0.02 0.05 26 98.92 0.02 0.02 0.05 0.05 0.04 0.01 0.02 27 98.96 0.01 0.04 0.00 0.00 0.03 0.04 0.03 28 98.49 0.09 0.03 0.02 0.07 0.06 0.04 0.01 29 98.92 0.01 0.01 0.03 0.00 0.02 0.01 0.03 30 99.37 0.04 0.03 0.00 0.00 0.04 0.03 0.00

MDL 0.05 0.05 0.05 0.16 0.15 0.04 0.03 0.07

Mean 0.08 0.00 0.05 0.05 0.00 Variance 0.00 0.00 0.00 Standard Deviation 0.02 0.01 0.01

98 CHI-CH-12 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.6 0.0 0.0 0.0 0.1 0.0 0.0 0.0 2 98.5 0.0 0.0 0.0 0.0 0.1 0.0 0.0 3 98.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4 99.3 0.1 0.0 0.0 0.1 0.0 0.0 0.0 5 98.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 6 97.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 7 97.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 8 95.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 9 95.7 0.0 0.0 0.0 0.1 0.0 0.0 0.0 10 97.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 11 98.8 0.1 0.0 0.0 0.0 0.1 0.0 0.0 12 98.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 13 98.8 0.0 0.0 0.1 0.1 0.0 0.0 0.0 14 98.5 0.0 0.0 0.0 0.1 0.0 0.0 0.0 15 98.3 0.1 0.0 0.0 0.0 0.0 0.0 0.0 16 98.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 17 98.5 0.1 0.0 0.0 0.0 0.0 0.0 0.0 18 98.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 19 98.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0 20 98.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 21 99.2 0.0 0.0 0.0 0.1 0.0 0.0 0.0 22 98.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 23 98.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 24 98.1 0.1 0.0 0.0 0.0 0.0 0.0 0.0 25 98.5 0.1 0.0 0.0 0.0 0.0 0.0 0.0 26 98.8 0.1 0.0 0.0 0.0 0.0 0.0 0.1 27 97.6 0.1 0.0 0.1 0.0 0.1 0.0 0.0 28 98.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 29 98.7 0.1 0.0 0.1 0.0 0.0 0.0 0.0 30 98.3 0.1 0.0 0.0 0.0 0.0 0.0 0.0

MDL 0.1 0.0 0.1 0.2 0.2 0.0 0.0 0.1

Mean 0.1 0.0 0.1 0.0 0.0 Variance 0.0 0.0 0.0 Standard Deviation 0.0 0.0

99 CHI-CH-103 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.24 0.27 0.02 0.05 0.00 0.04 0.04 0.06 2 97.85 0.34 0.02 0.07 0.05 0.04 0.06 0.04 3 98.34 0.10 0.03 0.08 0.07 0.04 0.02 0.04 4 98.59 0.17 0.02 0.01 0.00 0.02 0.06 0.01 5 98.74 0.19 0.04 0.00 0.00 0.08 0.01 0.03 6 98.69 0.09 0.04 0.00 0.04 0.03 0.00 0.00 7 98.20 0.18 0.02 0.00 0.01 0.02 0.04 0.05 8 98.59 0.15 0.01 0.00 0.02 0.04 0.02 0.03 9 98.19 0.22 0.03 0.05 0.05 0.04 0.07 0.02 10 98.35 0.07 0.02 0.00 0.04 0.05 0.03 0.05 11 98.04 0.26 0.03 0.01 0.07 0.08 0.07 0.07 12 99.18 0.14 0.01 0.08 0.00 0.07 0.03 0.04 13 97.75 0.19 0.03 0.05 0.06 0.06 0.08 0.03 14 97.07 0.34 0.04 0.00 0.00 0.09 0.09 0.09 15 97.97 0.15 0.00 0.09 0.08 0.15 0.03 0.02 16 96.11 0.18 0.05 0.02 0.01 0.05 0.02 0.01 17 95.41 0.11 0.04 0.00 0.00 0.04 0.02 0.05 18 97.27 0.06 0.00 0.00 0.07 0.05 0.03 0.03 19 96.33 0.39 0.05 0.00 0.00 0.09 0.09 0.07 20 98.30 0.13 0.05 0.00 0.00 0.08 0.01 0.04 21 98.91 0.12 0.02 0.03 0.00 0.08 0.03 0.05 22 98.59 0.37 0.03 0.01 0.00 0.06 0.07 0.03 23 97.98 0.15 0.03 0.00 0.08 0.04 0.01 0.01 24 97.88 0.20 0.02 0.02 0.07 0.04 0.04 0.01 25 98.58 0.14 0.02 0.09 0.00 0.03 0.03 0.04 26 98.07 0.10 0.01 0.00 0.00 0.03 0.02 0.03 27 98.38 0.04 0.02 0.00 0.02 0.01 0.02 0.06 28 97.91 0.08 0.00 0.02 0.04 0.03 0.03 0.00 29 97.22 0.30 0.03 0.00 0.00 0.05 0.09 0.02 30 97.69 0.45 0.04 0.01 0.01 0.03 0.07 0.04

MDL 0.05 0.05 0.05 0.16 0.15 0.04 0.03 0.07

Mean 0.19 0.00 0.07 0.07 0.08 Variance 0.01 0.00 0.00 Standard Deviation 0.10 0.03 0.02

100 CHI-CH-44 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 97.96 0.16 0.00 0.00 0.00 0.30 0.09 0.08 2 95.75 0.23 0.04 0.00 0.00 0.06 0.07 0.06 3 97.74 0.19 0.03 0.03 0.01 0.06 0.04 0.09 4 95.77 0.09 0.00 0.04 0.00 0.03 0.06 0.05 5 97.00 0.06 0.00 0.00 0.00 0.02 0.06 0.11 6 96.72 0.08 0.02 0.00 0.11 0.07 0.08 0.08 7 98.27 0.07 0.01 0.00 0.04 0.04 0.05 0.10 8 98.87 0.07 0.03 0.00 0.07 0.03 0.05 0.11 9 99.08 0.02 0.02 0.07 0.04 0.03 0.08 0.08 10 98.98 0.07 0.00 0.02 0.00 0.03 0.06 0.14 11 99.01 0.01 0.00 0.02 0.05 0.02 0.06 0.14 12 99.15 0.03 0.00 0.05 0.00 0.09 0.07 0.05 13 97.99 0.01 0.02 0.00 0.00 0.02 0.06 0.07 14 98.02 0.04 0.00 0.08 0.06 0.03 0.08 0.08 15 98.95 0.10 0.00 0.00 0.00 0.02 0.07 0.08 16 98.72 0.00 0.00 0.00 0.00 0.13 0.05 0.15 17 99.28 0.00 0.00 0.00 0.00 0.00 0.05 0.09 18 98.63 0.00 0.03 0.02 0.00 0.01 0.04 0.07 19 98.62 0.07 0.02 0.02 0.00 0.01 0.06 0.08 20 97.29 0.07 0.02 0.00 0.04 0.03 0.06 0.07 21 98.05 0.04 0.03 0.00 0.01 0.03 0.05 0.06 22 96.10 0.02 0.02 0.03 0.02 0.01 0.08 0.08 23 98.33 0.01 0.01 0.03 0.03 0.00 0.03 0.11 24 96.13 0.00 0.02 0.00 0.03 0.02 0.05 0.11 25 97.25 0.00 0.01 0.00 0.07 0.01 0.08 0.06 26 98.53 0.00 0.01 0.00 0.02 0.02 0.04 0.05 27 96.36 0.02 0.02 0.05 0.03 0.02 0.05 0.08 28 97.77 0.03 0.01 0.09 0.07 0.04 0.09 0.03 29 98.68 0.04 0.01 0.05 0.00 0.03 0.04 0.09 30 99.08 0.00 0.01 0.00 0.02 0.00 0.08 0.08

MDL 0.05 0.05 0.05 0.16 0.15 0.04 0.03 0.07

Mean 0.11 0.00 0.12 0.06 0.10 Variance 0.00 0.01 0.00 0.00 Standard Deviation 0.06 0.09 0.01 0.02

101 CHI-CH-39 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 100.12 0.07 0.04 0.02 0.03 0.06 0.01 0.01 2 99.17 0.02 0.01 0.00 0.04 0.07 0.06 0.07 3 100.72 0.02 0.03 0.07 0.00 0.05 0.03 0.14 4 99.33 0.03 0.01 0.00 0.00 0.00 0.04 0.08 5 99.45 0.00 0.00 0.00 0.00 0.04 0.02 0.04 6 99.69 0.02 0.00 0.00 0.02 0.00 0.07 0.04 7 99.39 0.00 0.02 0.02 0.00 0.03 0.06 0.07 8 99.75 0.00 0.00 0.07 0.00 0.02 0.07 0.11 9 99.66 0.00 0.02 0.00 0.00 0.04 0.07 0.10 10 99.72 0.01 0.00 0.03 0.00 0.04 0.09 0.07 11 100.14 0.00 0.00 0.02 0.00 0.05 0.08 0.10 12 100.00 0.00 0.03 0.02 0.02 0.04 0.05 0.09 13 99.75 0.00 0.02 0.00 0.00 0.02 0.06 0.10 14 99.41 0.01 0.00 0.00 0.08 0.04 0.09 0.09 15 100.23 0.00 0.02 0.00 0.04 0.05 0.06 0.08 16 99.64 0.00 0.00 0.01 0.05 0.05 0.06 0.09 17 99.45 0.00 0.04 0.02 0.00 0.04 0.08 0.10 18 99.30 0.01 0.00 0.00 0.00 0.00 0.07 0.08 19 99.44 0.00 0.01 0.02 0.00 0.03 0.06 0.07 20 99.46 0.00 0.01 0.00 0.00 0.01 0.05 0.08 21 99.64 0.00 0.00 0.04 0.00 0.01 0.06 0.06 22 99.68 0.02 0.02 0.00 0.05 0.03 0.07 0.10 23 100.35 0.02 0.03 0.00 0.02 0.02 0.04 0.08 24 99.64 0.00 0.01 0.00 0.00 0.01 0.04 0.10 25 99.09 0.00 0.01 0.00 0.00 0.05 0.08 0.09 26 98.05 0.01 0.00 0.00 0.00 0.02 0.04 0.09 27 99.61 0.00 0.01 0.04 0.00 0.02 0.06 0.07 28 97.04 0.02 0.03 0.00 0.00 0.05 0.05 0.09 29 98.03 0.00 0.00 0.01 0.04 0.01 0.07 0.08 30 99.27 0.03 0.04 0.04 0.00 0.04 0.06 0.07

MDL 0.05 0.05 0.05 0.18 0.18 0.04 0.03 0.07

Mean 0.00 0.00 0.05 0.06 0.09 Variance 0.00 0.00 0.00 Standard Deviation 0.01 0.01 0.02

102 CHI-CH-23 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.26 0.01 0.00 0.00 0.06 0.00 0.01 0.03 2 98.27 0.02 0.00 0.00 0.00 0.02 0.01 0.03 3 98.05 0.02 0.01 0.00 0.00 0.04 0.05 0.01 4 97.86 0.01 0.02 0.01 0.03 0.01 0.05 0.07 5 98.74 0.03 0.02 0.03 0.05 0.03 0.01 0.01 6 98.58 0.01 0.00 0.11 0.03 0.02 0.03 0.02 7 98.58 0.00 0.00 0.00 0.06 0.01 0.04 0.05 8 98.65 0.00 0.00 0.05 0.04 0.01 0.05 0.05 9 98.28 0.04 0.00 0.07 0.00 0.02 0.03 0.03 10 97.51 0.00 0.00 0.01 0.00 0.00 0.05 0.01 11 98.70 0.01 0.00 0.02 0.10 0.00 0.04 0.01 12 97.73 0.02 0.00 0.10 0.06 0.01 0.01 0.01 13 98.66 0.02 0.02 0.00 0.02 0.02 0.00 0.00 14 97.93 0.00 0.01 0.00 0.00 0.00 0.05 0.04 15 98.26 0.01 0.00 0.02 0.00 0.02 0.00 0.00 16 98.69 0.06 0.00 0.00 0.00 0.01 0.04 0.01 17 97.46 0.10 0.00 0.05 0.04 0.03 0.04 0.00 18 97.77 0.03 0.00 0.00 0.00 0.02 0.05 0.07 19 98.48 0.00 0.00 0.00 0.09 0.00 0.02 0.02 20 98.66 0.01 0.00 0.00 0.01 0.03 0.00 0.03 21 98.36 0.03 0.00 0.02 0.00 0.04 0.04 0.04 22 98.25 0.00 0.00 0.00 0.00 0.01 0.04 0.02 23 98.48 0.00 0.00 0.00 0.10 0.00 0.02 0.07 24 98.81 0.01 0.00 0.03 0.02 0.02 0.04 0.05 25 98.47 0.02 0.00 0.00 0.06 0.05 0.05 0.02 26 98.88 0.10 0.03 0.09 0.04 0.04 0.04 0.02 27 99.16 0.03 0.00 0.02 0.00 0.01 0.03 0.03 28 98.56 0.07 0.01 0.00 0.04 0.03 0.04 0.04 29 98.17 0.01 0.00 0.00 0.00 0.00 0.04 0.03 30 98.60 0.10 0.01 0.00 0.00 0.04 0.04 0.01

MDL 0.05 0.05 0.05 0.17 0.18 0.04 0.03 0.07

Mean 0.09 0.00 0.04 0.04 0.07 Variance 0.00 0.00 0.00 Standard Deviation 0.02 0.00 0.01

103 SFI-CH-1A Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.24 0.02 0.00 0.02 0.05 0.00 0.00 0.00 2 98.86 0.03 0.00 0.04 0.00 0.00 0.01 0.01 3 99.52 0.01 0.01 0.00 0.03 0.00 0.01 0.01 4 99.04 0.03 0.00 0.00 0.00 0.04 0.01 0.00 5 98.37 0.00 0.00 0.00 0.00 0.01 0.00 0.00 6 98.71 0.03 0.04 0.00 0.00 0.01 0.00 0.00 7 99.30 0.01 0.00 0.05 0.05 0.01 0.00 0.00 8 99.41 0.04 0.00 0.00 0.04 0.04 0.04 0.03 9 98.64 0.02 0.02 0.09 0.00 0.04 0.02 0.00 10 99.50 0.00 0.00 0.03 0.01 0.02 0.00 0.02 11 99.55 0.00 0.00 0.02 0.05 0.01 0.02 0.03 12 99.12 0.06 0.00 0.00 0.10 0.00 0.02 0.01 13 98.70 0.05 0.00 0.00 0.07 0.03 0.00 0.02 14 99.24 0.04 0.01 0.00 0.03 0.02 0.02 0.00 15 99.85 0.04 0.02 0.06 0.07 0.03 0.01 0.00 16 99.46 0.02 0.01 0.03 0.00 0.00 0.00 0.02 17 99.31 0.01 0.00 0.00 0.00 0.01 0.01 0.01 18 98.91 0.07 0.00 0.06 0.00 0.03 0.02 0.00 19 99.56 0.05 0.00 0.00 0.00 0.01 0.01 0.01 20 99.47 0.01 0.00 0.00 0.00 0.00 0.00 0.00 21 99.66 0.00 0.00 0.00 0.07 0.02 0.00 0.04 22 99.23 0.03 0.01 0.06 0.00 0.00 0.00 0.03 23 99.59 0.04 0.00 0.02 0.00 0.01 0.03 0.01 24 99.53 0.03 0.02 0.02 0.00 0.01 0.00 0.00 25 99.33 0.06 0.02 0.03 0.00 0.02 0.01 0.02 26 98.98 0.02 0.02 0.01 0.00 0.03 0.01 0.01 27 99.14 0.03 0.00 0.00 0.00 0.01 0.00 0.00 28 99.56 0.00 0.00 0.00 0.04 0.02 0.00 0.04 29 99.57 0.04 0.00 0.01 0.00 0.03 0.01 0.00 30 99.65 0.02 0.00 0.05 0.00 0.04 0.01 0.00

MDL 0.05 0.05 0.05 0.18 0.18 0.04 0.03 0.07

Mean 0.05 0.00 0.00 0.04 0.00 Variance 0.00 Standard Deviation 0.02

104 SFI-CH-FA Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 99.15 0.18 0.02 0.02 0.00 0.02 0.09 0.02 2 98.36 0.05 0.00 0.02 0.08 0.05 0.04 0.02 3 99.14 0.04 0.00 0.00 0.00 0.00 0.02 0.01 4 98.40 0.02 0.00 0.00 0.05 0.00 0.00 0.00 5 98.52 0.05 0.00 0.00 0.01 0.00 0.04 0.02 6 98.35 0.07 0.00 0.02 0.00 0.02 0.02 0.00 7 99.82 0.00 0.03 0.02 0.03 0.01 0.01 0.00 8 99.96 0.10 0.00 0.06 0.00 0.03 0.05 0.03 9 100.03 0.04 0.00 0.03 0.00 0.04 0.02 0.02 10 99.30 0.02 0.00 0.00 0.04 0.02 0.02 0.02 11 99.45 0.03 0.00 0.06 0.13 0.02 0.01 0.01 12 99.64 0.03 0.00 0.02 0.10 0.07 0.03 0.00 13 99.95 0.04 0.00 0.03 0.01 0.02 0.01 0.00 14 99.87 0.02 0.01 0.00 0.00 0.03 0.04 0.01 15 99.61 0.03 0.02 0.00 0.03 0.02 0.00 0.02 16 99.48 0.01 0.00 0.10 0.00 0.04 0.00 0.00 17 99.53 0.00 0.00 0.00 0.00 0.02 0.01 0.01 18 99.30 0.03 0.00 0.00 0.05 0.04 0.02 0.00 19 100.08 0.01 0.00 0.00 0.00 0.01 0.02 0.01 20 100.30 0.10 0.00 0.00 0.02 0.01 0.04 0.01 21 100.03 0.04 0.01 0.01 0.00 0.02 0.03 0.02 22 99.59 0.04 0.00 0.00 0.01 0.02 0.01 0.06 23 99.56 0.02 0.00 0.00 0.00 0.01 0.01 0.18 24 100.06 0.03 0.00 0.03 0.00 0.00 0.04 0.00 25 100.46 0.02 0.02 0.05 0.23 0.01 0.00 0.03 26 100.10 0.00 0.02 0.00 0.06 0.04 0.01 0.00 27 99.36 0.02 0.01 0.00 0.00 0.02 0.01 0.00 28 99.81 0.00 0.00 0.04 0.00 0.02 0.03 0.00 29 99.50 0.02 0.00 0.13 0.09 0.02 0.02 0.00 30 99.08 0.06 0.02 0.00 0.00 0.16 0.03 0.02

MDL 0.05 0.05 0.05 0.18 0.18 0.04 0.03 0.07

Mean 0.09 0.00 0.23 0.07 0.02 0.18 Variance 0.00 0.00 0.00 Standard Deviation 0.05 0.05 0.02

105 SFI-CH-FB Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 100.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2 100.0 0.1 0.0 0.1 0.0 0.0 0.0 0.0 3 100.1 0.1 0.0 0.0 0.0 0.0 0.1 0.0 4 99.6 0.1 0.0 0.1 0.0 0.0 0.1 0.0 5 99.7 0.0 0.0 0.1 0.0 0.0 0.0 0.0 6 99.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 7 99.7 0.1 0.0 0.0 0.0 0.0 0.0 0.0 8 99.8 0.0 0.0 0.0 0.1 0.0 0.0 0.0 9 99.4 0.1 0.0 0.0 0.0 0.0 0.0 0.0 10 99.6 0.2 0.0 0.0 0.1 0.1 0.1 0.0 11 99.8 0.1 0.0 0.0 0.1 0.1 0.1 0.0 12 99.1 0.0 0.0 0.1 0.0 0.0 0.0 0.0 13 99.8 0.1 0.0 0.0 0.1 0.0 0.0 0.0 14 97.5 0.1 0.0 0.0 0.0 0.0 0.1 0.0 15 97.5 0.2 0.0 0.0 0.0 0.1 0.1 0.0 16 100.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0 17 99.8 0.1 0.0 0.1 0.0 0.0 0.0 0.0 18 99.9 0.1 0.0 0.0 0.0 0.1 0.0 0.0 19 100.0 0.1 0.0 0.1 0.0 0.0 0.0 0.0 20 99.8 0.1 0.0 0.0 0.0 0.0 0.0 0.0 21 99.8 0.1 0.0 0.0 0.0 0.0 0.1 0.0 22 100.1 0.1 0.0 0.0 0.0 0.0 0.0 0.0 23 99.9 0.3 0.0 0.0 0.0 0.0 0.1 0.0 24 99.7 0.1 0.0 0.0 0.0 0.0 0.0 0.0 25 99.9 0.1 0.0 0.0 0.0 0.1 0.1 0.0 26 99.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 27 100.1 0.1 0.0 0.0 0.0 0.0 0.0 0.0 28 99.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 29 99.9 0.1 0.0 0.0 0.0 0.0 0.0 0.0 30 100.1 0.1 0.0 0.0 0.0 0.1 0.0 0.0

MDL 0.1 0.0 0.1 0.2 0.2 0.0 0.0 0.1

Mean 0.1 0.0 0.1 0.1 0.0 Variance 0.0 0.0 0.0 Standard Deviation 0.1 0.0 0.0

106 SFI-CH-1K.4 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.71 0.05 0.00 0.00 0.00 0.00 0.00 0.01 2 98.39 0.04 0.01 0.00 0.03 0.01 0.01 0.00 3 97.27 0.09 0.00 0.00 0.00 0.02 0.01 0.02 4 97.62 0.08 0.00 0.02 0.00 0.01 0.06 0.02 5 97.85 0.17 0.00 0.02 0.00 0.05 0.06 0.00 6 95.23 0.25 0.00 0.02 0.06 0.06 0.06 0.03 7 94.87 0.28 0.00 0.05 0.03 0.08 0.07 0.03 8 97.94 0.17 0.01 0.05 0.00 0.05 0.08 0.01 9 97.66 0.05 0.04 0.02 0.00 0.04 0.03 0.00 10 98.03 0.04 0.00 0.00 0.09 0.02 0.04 0.03 11 97.71 0.07 0.00 0.00 0.03 0.02 0.02 0.00 12 97.06 0.04 0.00 0.01 0.05 0.04 0.00 0.03 13 95.53 0.03 0.00 0.00 0.00 0.01 0.03 0.02 14 93.87 0.00 0.02 0.00 0.00 0.00 0.03 0.05 15 97.62 0.00 0.00 0.03 0.08 0.04 0.03 0.00 16 96.75 0.02 0.00 0.00 0.00 0.00 0.01 0.04 17 96.46 0.02 0.01 0.02 0.10 0.03 0.04 0.02 18 97.81 0.03 0.00 0.05 0.04 0.02 0.04 0.03 19 97.39 0.04 0.00 0.10 0.01 0.05 0.04 0.00 20 97.27 0.00 0.01 0.03 0.01 0.01 0.01 0.00 21 97.55 0.02 0.00 0.00 0.00 0.01 0.04 0.02 22 97.27 0.09 0.00 0.02 0.00 0.01 0.08 0.01 23 98.07 0.11 0.00 0.01 0.00 0.01 0.06 0.00 24 97.91 0.09 0.01 0.08 0.00 0.03 0.06 0.01 25 97.48 0.14 0.01 0.00 0.11 0.02 0.06 0.04 26 97.55 0.01 0.00 0.05 0.04 0.02 0.01 0.01 27 96.28 0.34 0.00 0.00 0.00 0.06 0.08 0.01 28 98.05 0.16 0.00 0.00 0.09 0.02 0.08 0.03 29 97.81 0.04 0.01 0.02 0.02 0.01 0.03 0.00 30 97.83 0.07 0.01 0.00 0.04 0.00 0.06 0.03

MDL 0.05 0.05 0.05 0.17 0.15 0.04 0.04 0.08

Mean 0.13 0.00 0.06 0.06 0.00 Variance 0.01 0.00 0.00 Standard Deviation 0.02

107 SFI-CH-1E Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 97.28 0.15 0.02 0.00 0.00 0.04 0.11 0.02 2 96.23 0.03 0.01 0.02 0.00 0.04 0.03 0.02 3 96.80 0.03 0.01 0.02 0.07 0.01 0.06 0.00 4 96.03 0.06 0.02 0.02 0.00 0.03 0.05 0.00 5 95.42 0.06 0.01 0.01 0.00 0.05 0.07 0.03 6 95.66 0.03 0.00 0.00 0.00 0.06 0.06 0.01 7 95.91 0.02 0.00 0.04 0.00 0.04 0.06 0.01 8 97.35 0.01 0.01 0.07 0.00 0.03 0.06 0.00 9 97.61 0.01 0.00 0.09 0.00 0.03 0.04 0.00 10 97.35 0.01 0.00 0.01 0.00 0.04 0.00 0.02 11 96.84 0.04 0.01 0.00 0.04 0.05 0.01 0.04 12 97.66 0.01 0.01 0.00 0.04 0.05 0.01 0.01 13 96.96 0.13 0.00 0.00 0.04 0.03 0.09 0.03 14 97.44 0.01 0.00 0.01 0.03 0.01 0.03 0.00 15 97.76 0.03 0.01 0.00 0.06 0.05 0.04 0.01 16 97.27 0.00 0.00 0.00 0.12 0.01 0.01 0.01 17 97.39 0.02 0.01 0.02 0.02 0.04 0.00 0.03 18 97.54 0.09 0.00 0.00 0.07 0.05 0.06 0.00 19 96.55 0.02 0.01 0.07 0.00 0.06 0.03 0.02 20 97.29 0.11 0.02 0.00 0.06 0.03 0.06 0.00 21 97.58 0.00 0.00 0.02 0.04 0.03 0.00 0.00 22 97.63 0.02 0.00 0.13 0.00 0.01 0.02 0.02 23 97.45 0.04 0.03 0.02 0.00 0.06 0.07 0.00 24 97.88 0.02 0.00 0.00 0.03 0.04 0.00 0.02 25 97.43 0.00 0.00 0.01 0.00 0.04 0.02 0.00 26 96.99 0.03 0.02 0.01 0.02 0.06 0.00 0.00 27 98.67 0.04 0.00 0.00 0.00 0.03 0.03 0.00 28 98.57 0.03 0.00 0.04 0.03 0.04 0.01 0.04 29 98.53 0.00 0.00 0.04 0.00 0.06 0.03 0.00 30 98.45 0.04 0.00 0.06 0.04 0.02 0.01 0.01

MDL 0.05 0.05 0.05 0.17 0.15 0.04 0.04 0.08

Mean 0.10 0.00 0.05 0.06 0.00 Variance 0.00 0.00 0.00 Standard Deviation 0.01 0.02

108 SFI-CH-1H Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.48 0.02 0.00 0.01 0.04 0.04 0.02 0.04 2 98.35 0.00 0.00 0.00 0.01 0.02 0.02 0.01 3 97.87 0.14 0.00 0.01 0.06 0.04 0.08 0.02 4 98.90 0.05 0.02 0.05 0.00 0.00 0.02 0.01 5 98.60 0.03 0.01 0.05 0.08 0.00 0.02 0.01 6 97.78 0.04 0.00 0.09 0.00 0.01 0.04 0.02 7 98.63 0.06 0.00 0.00 0.13 0.05 0.03 0.00 8 98.26 0.13 0.00 0.09 0.00 0.06 0.06 0.03 9 98.48 0.04 0.00 0.08 0.05 0.00 0.04 0.01 10 98.38 0.05 0.00 0.00 0.08 0.04 0.04 0.00 11 98.49 0.00 0.03 0.00 0.03 0.02 0.00 0.01 12 98.20 0.01 0.01 0.00 0.00 0.02 0.02 0.01 13 97.45 0.05 0.01 0.00 0.04 0.02 0.01 0.00 14 97.10 0.04 0.00 0.08 0.06 0.02 0.03 0.03 15 98.03 0.00 0.00 0.01 0.02 0.01 0.02 0.01 16 98.66 0.03 0.00 0.05 0.00 0.00 0.01 0.01 17 98.13 0.00 0.02 0.06 0.00 0.03 0.03 0.02 18 98.19 0.04 0.00 0.04 0.03 0.03 0.04 0.00 19 97.94 0.08 0.02 0.03 0.00 0.03 0.03 0.00 20 98.52 0.02 0.00 0.00 0.07 0.02 0.03 0.00 21 97.98 0.02 0.00 0.07 0.03 0.00 0.01 0.00 22 98.40 0.02 0.00 0.05 0.00 0.04 0.03 0.00 23 98.12 0.02 0.00 0.02 0.00 0.00 0.00 0.01 24 98.32 0.00 0.00 0.00 0.04 0.02 0.05 0.02 25 98.52 0.01 0.00 0.02 0.01 0.02 0.03 0.00 26 98.33 0.02 0.00 0.00 0.00 0.04 0.02 0.00 27 97.72 0.05 0.00 0.00 0.00 0.01 0.08 0.00 28 98.35 0.01 0.00 0.01 0.00 0.03 0.04 0.02 29 97.94 0.02 0.00 0.00 0.02 0.00 0.07 0.02 30 98.75 0.05 0.00 0.05 0.06 0.00 0.03 0.00

MDL 0.05 0.05 0.05 0.17 0.15 0.04 0.04 0.08

Mean 0.08 0.00 0.05 0.05 0.00 Variance 0.00 0.00 0.00 Standard Deviation 0.01 0.02

109 PRI-CH-25 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 96.22 0.16 0.56 0.05 0.00 0.11 0.05 0.02 2 97.86 0.04 0.01 0.00 0.04 0.03 0.03 0.02 3 96.20 0.05 0.48 0.00 0.00 0.65 0.04 0.00 4 97.45 0.01 0.03 0.00 0.00 0.02 0.01 0.02 5 96.72 0.12 0.01 0.00 0.00 0.02 0.05 0.01 6 81.58 0.06 3.29 0.00 0.03 5.30 0.01 0.05 7 93.62 0.13 0.11 0.04 0.11 0.20 0.09 0.00 8 90.20 0.08 1.58 0.08 0.00 2.09 0.10 0.03 9 89.01 0.10 2.19 0.04 0.00 3.00 0.02 0.02 10 79.77 0.09 3.81 0.01 0.05 6.40 0.02 0.03 11 98.13 0.03 0.02 0.04 0.02 0.02 0.00 0.05 12 89.53 0.09 1.69 0.00 0.00 2.41 0.04 0.02 13 96.91 0.20 0.35 0.00 0.00 0.35 0.07 0.04 14 97.77 0.00 0.01 0.00 0.00 0.01 0.01 0.03 15 98.07 0.03 0.01 0.00 0.00 0.00 0.01 0.02 16 97.23 0.08 0.06 0.04 0.03 0.04 0.02 0.02 17 96.88 0.06 0.19 0.03 0.00 0.38 0.03 0.00 18 97.89 0.11 0.03 0.00 0.00 0.07 0.04 0.02 19 90.72 0.04 1.45 0.05 0.00 2.31 0.02 0.03 20 85.95 0.03 2.56 0.00 0.07 4.61 0.01 0.02 21 79.12 0.01 3.96 0.06 0.08 6.85 0.03 0.01 22 97.43 0.06 0.07 0.02 0.00 0.10 0.03 0.03 23 97.38 0.04 0.03 0.10 0.04 0.05 0.00 0.02 24 96.75 0.05 0.27 0.04 0.01 0.27 0.00 0.02 25 97.98 0.04 0.01 0.00 0.00 0.03 0.03 0.01 26 97.07 0.09 0.20 0.01 0.03 0.38 0.00 0.03 27 96.53 0.14 0.24 0.00 0.00 0.38 0.06 0.05 28 98.03 0.09 0.04 0.02 0.00 0.03 0.02 0.04 29 98.15 0.01 0.00 0.00 0.00 0.03 0.02 0.00 30 91.68 0.07 1.48 0.01 0.04 2.49 0.01 0.02

MDL 0.05 0.05 0.05 0.17 0.15 0.04 0.04 0.08

Mean 0.09 1.29 1.83 0.06 0.00 Variance 0.00 1.74 4.93 0.00 Standard Deviation 0.03 1.32 2.22 0.02

110

PRI-CH-12 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 94.39 0.28 0.71 0.00 0.10 1.12 0.05 0.02 2 93.34 0.08 0.86 0.07 0.00 1.35 0.02 0.03 3 87.16 0.14 2.12 0.08 0.09 3.83 0.09 0.03 4 80.25 0.18 3.39 0.04 0.00 6.02 0.05 0.03 5 82.99 0.10 2.88 0.00 0.06 4.98 0.04 0.00 6 94.79 0.08 0.31 0.00 0.11 0.11 0.02 0.03 7 96.27 0.16 0.26 0.01 0.00 0.39 0.05 0.00 8 89.75 0.08 1.43 0.06 0.01 2.15 0.01 0.03 9 63.50 0.15 6.57 0.06 0.15 12.16 0.09 0.03 10 62.00 0.05 6.35 0.05 0.10 13.14 0.01 0.02 11 96.72 0.13 0.24 0.00 0.00 0.23 0.06 0.00 12 95.10 0.18 0.38 0.06 0.06 0.53 0.06 0.01 13 96.20 0.09 0.37 0.03 0.00 0.54 0.09 0.01 14 95.12 0.17 0.39 0.00 0.00 0.43 0.08 0.00 15 92.22 0.13 0.96 0.01 0.07 1.95 0.07 0.04 16 95.81 0.27 0.04 0.00 0.00 0.11 0.13 0.04 17 86.61 0.09 2.21 0.01 0.00 3.60 0.02 0.00 18 86.72 0.15 2.10 0.04 0.03 3.71 0.05 0.03 19 96.29 0.17 0.16 0.03 0.02 0.07 0.06 0.04 20 87.17 0.12 0.26 0.00 0.00 5.78 0.02 0.00 21 87.14 0.14 2.19 0.05 0.00 3.91 0.10 0.04 22 84.16 0.05 2.84 0.03 0.03 4.91 0.03 0.02 23 95.77 0.10 0.27 0.05 0.00 0.51 0.05 0.04 24 96.15 0.18 0.28 0.07 0.00 0.91 0.07 0.03 25 91.69 0.17 0.87 0.03 0.02 1.77 0.11 0.02 26 95.65 0.19 0.12 0.00 0.00 0.15 0.11 0.02 27 96.65 0.10 0.03 0.00 0.02 0.17 0.03 0.00 28 66.89 0.03 5.77 0.02 0.06 11.11 0.03 0.00 29 84.07 0.01 2.68 0.00 0.05 4.88 0.02 0.01 30 85.96 0.04 2.50 0.09 0.00 4.33 0.01 0.03

MDL 0.05 0.05 0.05 0.17 0.15 0.04 0.04 0.08

Mean 0.14 1.77 3.16 0.07 0.00 Variance 0.00 3.52 13.05 0.00 Standard Deviation 0.06 1.88 3.61 0.03

111

PRI-CH-16 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.27 0.08 0.00 0.02 0.05 0.02 0.01 0.02 2 98.53 0.06 0.03 0.00 0.04 0.05 0.00 0.01 3 98.08 0.06 0.12 0.00 0.00 0.04 0.01 0.02 4 97.90 0.06 0.06 0.00 0.02 0.06 0.04 0.01 5 97.92 0.06 0.06 0.00 0.00 0.03 0.04 0.02 6 98.26 0.09 0.07 0.07 0.00 0.10 0.04 0.02 7 97.57 0.07 0.04 0.05 0.00 0.05 0.00 0.00 8 98.59 0.01 0.03 0.00 0.09 0.02 0.01 0.00 9 98.11 0.06 0.04 0.00 0.01 0.00 0.05 0.00 10 98.81 0.00 0.03 0.02 0.00 0.04 0.02 0.03 11 98.62 0.04 0.08 0.08 0.00 0.11 0.02 0.02 12 98.64 0.07 0.03 0.00 0.06 0.05 0.03 0.01 13 98.40 0.06 0.08 0.00 0.06 0.16 0.03 0.00 14 98.33 0.04 0.05 0.00 0.07 0.07 0.03 0.01 15 98.16 0.16 0.07 0.02 0.00 0.03 0.05 0.03 16 98.13 0.11 0.09 0.00 0.00 0.08 0.05 0.05 17 98.80 0.08 0.04 0.02 0.00 0.02 0.08 0.00 18 98.07 0.08 0.08 0.00 0.02 0.10 0.01 0.00 19 98.76 0.03 0.00 0.08 0.00 0.02 0.00 0.01 20 98.55 0.09 0.06 0.04 0.02 0.08 0.03 0.01 21 99.10 0.04 0.02 0.11 0.02 0.02 0.01 0.01 22 95.50 0.06 0.03 0.05 0.00 0.03 0.04 0.01 23 98.92 0.05 0.04 0.00 0.00 0.02 0.02 0.00 24 98.07 0.09 0.15 0.00 0.00 0.28 0.01 0.03 25 97.66 0.06 0.00 0.00 0.07 0.02 0.03 0.01 26 98.17 0.08 0.08 0.09 0.00 0.10 0.02 0.00 27 97.90 0.09 0.16 0.00 0.07 0.22 0.05 0.01 28 98.52 0.14 0.04 0.00 0.00 0.05 0.03 0.02 29 98.11 0.06 0.07 0.00 0.00 0.05 0.04 0.00 30 98.54 0.07 0.00 0.00 0.00 0.03 0.03 0.02

MDL 0.05 0.04 0.05 0.19 0.17 0.04 0.04 0.07

Mean 0.08 0.09 0.10 0.06 0.00 Variance 0.00 0.00 0.00 0.00 Standard Deviation 0.03 0.03 0.07 0.01

112

PRI-CH-14 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.84 0.00 0.00 0.00 0.04 0.01 0.00 0.03 2 97.84 0.01 0.01 0.05 0.03 0.02 0.01 0.00 3 98.59 0.00 0.03 0.08 0.00 0.01 0.00 0.00 4 99.07 0.00 0.01 0.00 0.10 0.02 0.02 0.00 5 98.86 0.00 0.02 0.02 0.00 0.04 0.00 0.01 6 98.53 0.02 0.02 0.05 0.02 0.02 0.00 0.00 7 98.56 0.00 0.02 0.02 0.00 0.03 0.00 0.04 8 99.00 0.03 0.00 0.01 0.00 0.02 0.01 0.00 9 97.78 0.01 0.01 0.01 0.00 0.04 0.01 0.01 10 98.13 0.04 0.00 0.00 0.00 0.02 0.01 0.00 11 97.87 0.03 0.03 0.06 0.01 0.04 0.01 0.00 12 98.35 0.02 0.00 0.00 0.05 0.01 0.03 0.01 13 97.52 0.02 0.05 0.00 0.04 0.31 0.00 0.03 14 98.52 0.04 0.01 0.00 0.05 0.00 0.01 0.00 15 98.11 0.03 0.01 0.00 0.00 0.04 0.00 0.00 16 98.93 0.01 0.00 0.00 0.00 0.01 0.04 0.02 17 98.47 0.04 0.06 0.00 0.03 0.03 0.01 0.02 18 98.36 0.02 0.02 0.11 0.02 0.02 0.00 0.04 19 98.66 0.01 0.02 0.00 0.04 0.05 0.00 0.03 20 98.20 0.01 0.01 0.03 0.00 0.01 0.02 0.02 21 98.68 0.03 0.02 0.00 0.00 0.05 0.04 0.01 22 98.65 0.01 0.03 0.00 0.00 0.02 0.01 0.00 23 96.59 0.03 0.04 0.06 0.03 0.06 0.01 0.04 24 97.98 0.02 0.00 0.00 0.00 0.09 0.02 0.00 25 98.13 0.06 0.06 0.00 0.04 0.08 0.02 0.00 26 97.52 0.02 0.03 0.00 0.07 0.05 0.02 0.02 27 98.61 0.02 0.00 0.10 0.00 0.02 0.02 0.00 28 98.63 0.01 0.02 0.00 0.03 0.01 0.03 0.03 29 97.72 0.00 0.03 0.00 0.00 0.03 0.05 0.00 30 98.59 0.02 0.07 0.01 0.00 0.09 0.04 0.00

MDL 0.05 0.04 0.05 0.19 0.17 0.04 0.04 0.07

Mean 0.06 0.07 0.09 0.04 0.00 Variance 0.00 0.01 0.00 Standard Deviation 0.01 0.08 0.01

113

PRI-CH-18 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 90.95 0.17 1.89 0.01 0.00 2.44 0.06 0.00 2 87.88 0.15 1.62 0.00 0.02 3.01 0.09 0.01 3 90.87 0.37 0.81 0.09 0.10 1.50 0.17 0.04 4 84.93 0.02 2.79 0.03 0.07 5.19 0.03 0.02 5 97.14 0.06 0.36 0.12 0.00 0.65 0.00 0.02 6 97.18 0.07 0.27 0.00 0.03 0.48 0.05 0.01 7 97.46 0.07 0.12 0.00 0.02 0.22 0.04 0.03 8 98.69 0.09 0.02 0.02 0.00 0.00 0.04 0.03 9 98.06 0.36 0.04 0.00 0.00 0.09 0.13 0.03 10 99.29 0.10 0.01 0.02 0.00 0.03 0.06 0.01 11 99.05 0.08 0.06 0.00 0.00 0.08 0.12 0.00 12 96.44 0.06 0.55 0.00 0.05 0.96 0.12 0.02 13 98.74 0.12 0.03 0.00 0.00 0.04 0.17 0.02 14 98.95 0.03 0.02 0.00 0.00 0.01 0.09 0.01 15 99.14 0.06 0.00 0.05 0.00 0.01 0.06 0.01 16 98.99 0.11 0.05 0.03 0.09 0.08 0.08 0.01 17 97.81 0.15 0.15 0.05 0.07 0.26 0.09 0.00 18 99.15 0.14 0.00 0.00 0.01 0.03 0.11 0.00 19 97.92 0.08 0.11 0.00 0.02 0.26 0.08 0.02 20 98.59 0.08 0.06 0.00 0.00 0.06 0.12 0.01 21 96.10 0.12 0.36 0.02 0.00 0.61 0.11 0.03 22 99.18 0.06 0.01 0.04 0.01 0.02 0.10 0.02 23 78.04 0.25 3.98 0.20 0.03 7.36 0.10 0.04 24 97.90 0.13 0.02 0.00 0.00 0.04 0.13 0.02 25 98.67 0.12 0.02 0.05 0.01 0.04 0.11 0.04 26 98.41 0.01 0.02 0.02 0.00 0.02 0.06 0.04 27 98.48 0.00 0.00 0.00 0.00 0.04 0.03 0.02 28 98.74 0.00 0.00 0.05 0.10 0.04 0.00 0.00 29 99.14 0.04 0.02 0.02 0.02 0.01 0.04 0.00 30 98.33 0.03 0.00 0.00 0.09 0.04 0.01 0.04

MDL 0.05 0.04 0.05 0.19 0.17 0.04 0.04 0.07

Mean 0.12 0.88 1.45 0.09 0.00 Variance 0.01 1.40 4.45 0.00 Standard Deviation 0.07 1.18 2.11 0.04

114

PRI-CH-49 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 98.34 0.02 0.00 0.00 0.00 0.06 0.01 0.04 2 97.86 0.01 0.02 0.07 0.09 0.03 0.00 0.00 3 98.17 0.04 0.02 0.00 0.00 0.06 0.01 0.02 4 98.13 0.02 0.02 0.00 0.06 0.04 0.01 0.00 5 97.98 0.02 0.03 0.07 0.01 0.04 0.04 0.00 6 98.35 0.03 0.03 0.04 0.00 0.00 0.00 0.00 7 98.43 0.02 0.04 0.00 0.00 0.06 0.02 0.02 8 98.75 0.05 0.03 0.00 0.00 0.02 0.01 0.02 9 99.01 0.03 0.02 0.00 0.00 0.06 0.00 0.02 10 97.09 0.06 0.04 0.00 0.00 0.04 0.00 0.00 11 95.96 0.04 0.11 0.00 0.00 0.68 0.02 0.02 12 98.37 0.03 0.02 0.03 0.00 0.05 0.00 0.00 13 98.04 0.02 0.00 0.02 0.07 0.03 0.00 0.00 14 98.45 0.01 0.04 0.01 0.14 0.02 0.07 0.03 15 98.00 0.00 0.02 0.00 0.00 0.09 0.01 0.00 16 98.30 0.02 0.02 0.00 0.00 0.01 0.06 0.02 17 97.52 0.03 0.00 0.00 0.02 0.03 0.05 0.00 18 98.05 0.01 0.02 0.08 0.00 0.05 0.07 0.05 19 97.06 0.01 0.00 0.00 0.02 0.04 0.04 0.01 20 97.70 0.02 0.00 0.01 0.00 0.06 0.01 0.02 21 97.23 0.00 0.03 0.00 0.05 0.04 0.07 0.01 22 97.93 0.02 0.04 0.00 0.00 0.11 0.08 0.02 23 97.85 0.02 0.03 0.00 0.00 0.03 0.07 0.00 24 98.24 0.01 0.03 0.05 0.02 0.01 0.08 0.00 25 98.08 0.06 0.00 0.00 0.02 0.06 0.04 0.00 26 98.38 0.00 0.01 0.00 0.00 0.05 0.10 0.00 27 97.35 0.05 0.03 0.05 0.02 0.01 0.10 0.00 28 97.52 0.05 0.02 0.06 0.01 0.04 0.02 0.02 29 96.83 0.02 0.05 0.06 0.08 0.03 0.07 0.00 30 97.16 0.03 0.02 0.10 0.02 0.09 0.05 0.00

MDL 0.05 0.04 0.05 0.19 0.17 0.04 0.04 0.07

Mean 0.05 0.08 0.11 0.07 0.00 Variance 0.00 0.00 0.03 0.00 Standard Deviation 0.01 0.04 0.16 0.02

115

PRI-CH-9 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 97.27 0.16 0.01 0.00 0.01 0.04 0.15 0.00 2 96.89 0.14 0.04 0.00 0.00 0.08 0.14 0.05 3 98.21 0.07 0.02 0.04 0.03 0.02 0.09 0.01 4 98.18 0.00 0.02 0.08 0.06 0.00 0.07 0.02 5 98.48 0.00 0.00 0.02 0.00 0.00 0.05 0.01 6 98.02 0.10 0.03 0.00 0.00 0.05 0.04 0.03 7 99.11 0.02 0.01 0.06 0.00 0.03 0.03 0.00 8 98.44 0.02 0.02 0.08 0.00 0.01 0.03 0.01 9 98.98 0.03 0.00 0.11 0.00 0.02 0.02 0.00 10 98.03 0.00 0.00 0.02 0.06 0.02 0.02 0.00 11 98.32 0.00 0.02 0.00 0.00 0.02 0.02 0.01 12 98.58 0.02 0.01 0.00 0.00 0.02 0.01 0.00 13 98.62 0.00 0.02 0.01 0.00 0.00 0.03 0.03 14 98.95 0.04 0.00 0.02 0.00 0.01 0.01 0.02 15 98.36 0.00 0.01 0.00 0.05 0.04 0.00 0.00 16 98.78 0.00 0.00 0.05 0.13 0.02 0.01 0.04 17 98.30 0.01 0.03 0.05 0.00 0.03 0.01 0.00 18 98.66 0.00 0.01 0.00 0.01 0.03 0.01 0.01 19 97.70 0.00 0.02 0.00 0.00 0.03 0.00 0.02 20 66.62 0.12 5.85 0.00 0.06 10.72 0.03 0.04 21 98.33 0.00 0.00 0.02 0.05 0.01 0.00 0.01 22 97.16 0.01 0.00 0.06 0.06 0.00 0.00 0.04 23 98.49 0.00 0.01 0.00 0.00 0.01 0.00 0.01 24 99.05 0.00 0.02 0.09 0.00 0.01 0.03 0.00 25 98.67 0.05 0.02 0.11 0.00 0.01 0.04 0.03 26 80.32 0.24 3.69 0.00 0.00 5.52 0.02 0.04 27 98.59 0.03 0.00 0.00 0.07 0.02 0.03 0.03 28 98.65 0.12 0.00 0.00 0.01 0.05 0.07 0.00 29 97.91 0.06 0.00 0.00 0.02 0.05 0.06 0.01 30 98.97 0.06 0.00 0.00 0.03 0.02 0.03 0.02

MDL 0.05 0.04 0.05 0.19 0.17 0.04 0.04 0.07

Mean 0.11 4.77 2.36 0.08 0.00 Variance 0.00 2.33 17.74 0.00 Standard Deviation 0.06 1.53 4.21 0.04

116

PRI-CH-3 Pt# SiO2 Al2O3 MgO FeO MnO CaO K2O Na2O 1 97.47 0.06 0.02 0.00 0.09 0.03 0.03 0.01 2 98.14 0.09 0.01 0.01 0.00 0.03 0.03 0.01 3 97.96 0.06 0.01 0.02 0.06 0.04 0.03 0.00 4 98.03 0.02 0.02 0.10 0.00 0.03 0.01 0.00 5 97.75 0.02 0.03 0.02 0.00 0.02 0.02 0.02 6 98.21 0.02 0.02 0.02 0.00 0.03 0.01 0.00 7 97.52 0.08 0.02 0.00 0.01 0.07 0.04 0.02 8 97.79 0.06 0.04 0.02 0.00 0.04 0.04 0.04 9 97.73 0.06 0.03 0.04 0.00 0.06 0.02 0.02 10 97.37 0.00 0.05 0.02 0.00 0.06 0.03 0.02 11 97.80 0.08 0.02 0.00 0.00 0.05 0.02 0.02 12 97.97 0.07 0.01 0.00 0.00 0.03 0.10 0.02 13 98.26 0.03 0.03 0.06 0.01 0.04 0.08 0.03 14 98.80 0.05 0.00 0.02 0.00 0.04 0.03 0.01 15 97.54 0.09 0.02 0.14 0.03 0.05 0.06 0.01 16 97.15 0.11 0.01 0.06 0.09 0.02 0.05 0.04 17 97.94 0.06 0.03 0.12 0.02 0.03 0.00 0.04 18 97.70 0.00 0.04 0.00 0.05 0.01 0.00 0.01 19 98.37 0.03 0.02 0.00 0.07 0.04 0.03 0.00 20 97.69 0.05 0.01 0.01 0.00 0.02 0.00 0.02 21 98.10 0.04 0.01 0.01 0.00 0.03 0.02 0.02 22 96.98 0.01 0.00 0.11 0.00 0.04 0.01 0.01 23 98.26 0.05 0.04 0.05 0.00 0.09 0.01 0.03 24 97.71 0.11 0.04 0.00 0.00 0.03 0.01 0.02 25 98.09 0.09 0.02 0.00 0.00 0.01 0.03 0.01 26 96.96 0.10 0.03 0.00 0.08 0.04 0.03 0.04 27 98.28 0.06 0.02 0.01 0.06 0.00 0.03 0.04 28 97.83 0.07 0.01 0.00 0.00 0.05 0.05 0.02 29 97.66 0.03 0.01 0.00 0.03 0.03 0.06 0.03 30 96.90 0.09 0.02 0.01 0.03 0.01 0.02 0.02

MDL 0.05 0.04 0.05 0.19 0.17 0.04 0.04 0.07

Mean 0.08 0.00 0.06 0.06 0.00 Variance 0.00 0.00 0.00 Standard Deviation 0.02 0.01 0.02

117 Appendix D. Stable isotope values of chert and host carbonate rock for all four quarries.

Chert Carbonate Host Rock d18O d13C d18O (VSMOW) dD (VSMOW) (VPDB) (VPDB) d18O (VSMOW) YOL CH34 21.29 -115.6 YOLO CH29 -6.79 -9.92 20.69 YOL CH20 21.68 -114.6 YOLO 20 -6.44 -9.05 21.58 YOL CH44 21.61 -112.8 YOLO CH44 -7.22 -10.08 20.52 YOL CH6 22.04 -117.6 YOLO CH6 -7.05 -8.68 21.97 YOL CH12 21.98 -116.4 YOLO CH11 -7.56 -8.41 22.24 CHI CH67 24.71 -108.6 CHI45 -4.86 -0.37 30.53 CHI CH12 26.8 -119.5 CHI 8 -3.27 -2.72 28.11 CHI CH35 22.83 -108.5 CHI 31 -3.28 -3.68 27.11 CHI CH84 22.43 -121.9 CHI 1 -8.75 -9.02 21.61 CHI CH23 28.15 -95.3 SFI 1D 21.96 -115.8 SFI 16 -4.45 -10.90 19.67 SFI FA 21.96 -112.9 SFI 1F -7.84 -8.90 21.73 SFI FB 22.01 -114.7 SFI 1H 21.63 -109.6 SFI 1E 22.02 -117.2 PRI CH49 24.27 -122.9 PRI CH49 -7.19 -6.54 24.16 PRI CH22 23.61 -116.6 PRI LS.2 -8.21 -9.87 20.74 PRI CH83 23.57 -121.5 PRI LS.1 -5.53 -3.98 26.80 PRI CH9 25.43 -113.1 PRI CH9 -5.86 -5.71 25.02 PRI CH17 27.43 -59.9

118