Biogeochemistry and Inorganic Geochemistry As Indicators of the Paleoenvironment and Paleohydrology of the Al-Azraq Basin, Jordan

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BIOGEOCHEMISTRY AND INORGANIC GEOCHEMISTRY AS INDICATORS OF THE PALEOENVIRONMENT AND PALEOHYDROLOGY OF THE AL-AZRAQ BASIN, JORDAN

A DISSERTATION IN GEOSCIENCES AND CHEMISTRY

Presented to the Faculty of the University of Missouri-Kansas City in partial of fulfillment of the requirements for the degree

Doctor of Philosophy

By Khaldoun Ibrahim Ahmad

BS University of Baghdad, 2000 MS University of Missouri-Kansas City, 2010

Kansas City, Missouri 2013

BIOGEOCHEMISTRY AND INORGANIC GEOCHEMISTRY AS INDICATORS

OF THE PALEOENVIRONMENT AND PALEOHYDROLOGY OF

THE AL-AZRAQ BASIN, JORDAN

Khaldoun Ahmad, Candidate for the Doctoral of Philosophy Degree

University of Missouri-Kansas City, 2013

ABSTRACT

This study investigates the biogeochemical and inorganic geochemical indicators for past environments and paleohydrology of a high resolution sediment record from the Al-Azraq Basin, Jordan. The second largest basin in Jordan, it is an important aquifer for a majority of the population in this arid region. Thirteen hundred samples were collected from fifty one meters of cored playa and lacustrine sediments. Stable isotopic composition of bulk organic matter and carbonate are the main proxies in addition to results from supporting methodologies including: grain size analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Based on the lithology of the core and geochemical data, the core is divided into three main zones: Zone 1 with six subzones; Zone 2 with four subzones; and Zone 3 with two subzones. Carbonate diagenesis by water enriched with sulfate occurs in Zone 1 and Zone 3, and affects the values of carbon isotopic compositions in some samples. Also, dolomitizition occurs in Zone 1, but does not affect the values of oxygen isotopic composition. Bulk organic matter revealed no effect of diagenesis except in

Zone 3b, which impacts the carbon isotopic composition values. Mineralogy and oxygen isotopic composition revealed the presence of low lake levels punctuated by dry periods during Zone 1. C/N ratios of bulk organic matter indicate the source of organic matter

primarily from aquatic algae in Zones 1a, 1b, and 1c; whereas Zone 1d indicates mixing of aquatic and terrestrial organic matter sources. This is considered a transition zone between marsh deposits and lake sediments. During this time the influx of materials to the basin increased, also indicating high precipitation and a wet climate. Zone 2 reveals changes in the climate by the presence of a lake during this period. Zone 3a exhibited the presence of marsh deposits as indicated by increasing abundant organic carbon concentrations. C/N ratios identify the presence of aquatic and land plants as the source of organic matter. Zone 3b represents a dry period from the presence of dolomite with increased sand particles and angular chert grains. This research identifies detailed environmental patterns of marsh to lake to playa environments with multiple cycles of seasonal deposition, indicative of significant climate shifts throughout the Middle to Late Pleistocene. Holocene age sediments are missing. The oxygen isotope record for the upper sediments correlate well with regional records from the eastern Mediterranean through Marine Isotope Stage (MIS 5). The base of the core dates between MIS 15 and 9 (570 to 300 ka) reflecting climates generally similar to a deglaciation.

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The faculties listed below, appointed by the Dean of the School of Graduate Studies, have examined a dissertation titled “ Biogeochemistry and inorganic geochemistry as indicators for the Paleoenvironment and Paleoclimate of the Al-Azraq Basin, Jordan”, presented by

Khaldoun Ahmad, candidate for the Doctor of Philosophy degree,and hereby certify that in their opinion it is worthy of acceptance.

Supervisory Committe

Caroline Davies, Ph.D., Committee Chair and Research Advisor Department of Geosciences

Raymond M. Coveney, Ph.D. Department of Geosciences

James Murowchick, Ph.D. Department of Geosciences

Nathan Oyler, Ph.D. Department of Chemistry

Kenneth Schmitz, Ph.D. Department of Chemistry

TABLE OF CONTENT

ABSTRACT ...... ii

LIST OF ILLUSTRATIONS ...... vii

LIST OF TABLES ...... x

AKNOWLEDGEMENTS...... ix

Chapter

1. INTRODUCTION

Introduction ...... 1

2. BIOGEOCHEMISTRY APPLICATIONS

Biogeochemistry ...... 6

Applications of Biogeochemistry for Paleoenvironments ...... 8

Stable Isotope Geochemisty ...... 10

Isotopes Definition and Notation ...... 10

Fractionation of Isotopes...... 12

Applications of Isotope Geochemistry for Paleoenvironmental Paleoclimate

Reconstructions ...... 13

Organic Matter in Lake Sediments ...... 13

Isotopes of Carbon and Nitrogen and C/N ratio in Lacustrine

Sediments ...... 16

Carbon and Oxygen Isotopes of Carbonate ...... 20

Carbonate in Salt Lake Sediments ...... 20

Oxygen and Carbone Isotopic Composition of Lacustrine

Sediments ...... 22

Oxygen Isotopes Fractionation in inorganic Carbone ...... 22

3. STUDY AREA AND BACKROUND RESEARCH

Introduction ...... 27

Geological Setting and Surficial Geology ...... 29

Distribution of Regional Tectonic and Geological Units ...... 29

Mineral Deposits Distribution...... 33

Al-Azraq Basin Overview and Description ...... 35

Introduction ...... 35

Geological Setting of Al-Azraq Basin ...... 36

Hydrology of Al-Azraq Basin ...... 37

Al-Azraq Climate ...... 39

Paleoenvironment and Paleoclimate of the Al-Azraq Basin ...... 40

Archaeology and Geoarcheology of Al-Azraq Basin ...... 41

Chronology of the Al-Azraq Basin ...... 43

4. INTERPRETATION OF LACUSTRIENE SEDIMENT AND APPLIED METHODS

Introduction ...... 47

Arid Lake Sediments...... 47

Organic Matter Content of Lacustrine Sediments (OC %) ...... 48

Sample Preparation ...... 49

13 Carbon Isotopic Composition of Lacustrine Organic Matter (δ Corg ‰) 49

Nitrogen Isotopic Composition of Lacustrine Organic

15 Matter (δ Norg ‰) ...... 51

C/N Ratio of Lacustrine Sediments ...... 52

Sample Isotope Preparation ...... 52

Stable Isotope Sample Procedure...... 53

13 Isotopic Composition of Calcium Carbonate (δ Ccarb‰) 56

Sample Preparation ...... 58

Magnetic Susceptibility ...... 59

Sample Preparation ...... 59

Inductively Coupled Plasma Atomic Emission Spectroscopy ......

(ICP-AES) ...... 59

Sample Preparation ...... 60

Grain Size Analysis...... 60

Smear Slide Technique ...... 64

Sample Procedure ...... 65

X-ray Diffraction ...... 66

Sample Procedure ...... 66

Summary ...... 67

5. RESULTS

Introduction ...... 68

Core Sediment Description ...... 68

Smear Slides...... 77

Grain Size Analysis...... 84

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Magnetic Susceptibility ...... 86

Organic Carbon Content (OC %) ...... 90

Total Nitrogen Percentage of Organic Matter (% Ntotal) ...... 90

13 Carbon Isotopic Composition of Organic Matter (δ Corg) ...... 92

15 Nitrogen Isotopic Composition (δ Norg) ...... 93

C/N Ratios of Organic Matter ...... 93

Calcium Carbonate content in Sediments (CaCO3 %) ...... 94

Oxygen and Carbon Isotopic Compositions of

13 18 Carbonate (δ Ccarb & δ Ocarb‰) ...... 95

Inductively Couple Plasma Atomic Emission Spectroscopy

(ICP-AES) ...... 96

6. STASTISTICs ANALYSIS RESULTS AND DISCUSSIONS

Introduction ...... 99

Cluster Analysis ...... 99

Cluster of Major and Trace Elements ...... 100

Cluster Analysis of Stable Isotopes Geochemistry Data ...... 103

7. DISCUSSION

Introduction ...... 105

Diagenesis of Organic Matter ...... 107

Diagenesis of Calcium Carbonate ...... 110

Mineral Weathering ...... 115

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Paleohydrology and Paleoenvironmental Interpretations ...... 116

Carbonate Minerals ...... 117

Primary and Secondary Calcium Carbonate ...... 119

Covariance of Carbonate Isotopes ...... 121

Paleohydrology and Paleolake Levels ...... 123

Paleoenvironmental Zones ...... 123

Paleoenvironment and Paleoproductivity ...... 130

Summary of Paleoclimate Implications ...... 136

8. CONCLUSIONS...... 141

Summary of Findings by Zone ...... 141

GLOSSARY ...... 144

APPENDICES ...... 145

A. Borehole Logs ...... 146

B. Grain Size Data and Classification ...... 164

C. XRD Patterns ...... 176

D. Carbon and Nitrogen Isotopic Composition of Bulk Organic

Matter Data ...... 180

E. Carbon and Oxygen Isotopic Composition of Calcium

Carbonate Data...... 191

F. Major and Trace Elements Geochemical Data ...... 199

G. Depth Correlation for Statistics ...... 209

REFERENCES ...... 213

VITA ...... 237

List of Illustrations

Figure Page

2.1 The relationship of oxygen and carbon isotopes ranges to C3 and C4 plants, and isotopes commonly preserved in lake sediments...... 15

2.2 Processes of organic matter production in lake sediments, and involving delivery of organic matter to sediments Meyers and Ishiwatari (1993) ...... 16

2.3 Organic matter production in lake sediments and carbon isotopic signature of each kind of organic matter in lake freshwater. Modified from Leng and Marshall (2004) ...... 17

2.4 Nitrogen isotopic composition of fresh water. Modified from Leng and Marshall (2004) ...... 18

2.5 Factors impacting the oxygen isotopic composition of carbonate. Modified from Leng and Marshall (2004) ...... 24

3.1 Map and Google image of the area of study in Al-Azraq Basin. Location of sediments cores Az1 and Az3 within the Qa Al-Azraq ...... 28

3.2 Isohyet map of mean annual precipitation in millimeters (mm). The highest precipitation is along the escarpment of the Jordan Plateau. Modified from Water for the Future, NAP (1999). Data sources from information in Salameh and Bannayan (1993) and the U.S. Central Intelligence Agency (1993) ...... 30

3.3 Diagram showing the three tectonic plates and the distribution of regional faults in Jordan Plateau. Modified from Natural Resources Authority, Amman, Jordan ...... 32

3.4 Mineral distributions in Jordan. Modified from Natural Resources Authority, Amman, Jordan ...... 35 3.5 Distribution of the drainages into the Al-Azraq basin. Modified from Naqa (2010) ...... 38

3.6 Al-Azraq Basin in flood stage during winter time in 2010. The picture in the top is the flooded during winter time October 2010. Adapted from Naqa (2010). The pictures in the bottom show the flooded in October 1998 ...... 39 3.7 The chronology of the Al-Azraq sediments. Gray line based on single radiocarbon date of calcite at 6.3 meters below the surface (Cane, 1992);

Black-dash line based on three IRSL ages at 0.28 m, 5.46 m, and 11.66 m (Davies, 2005b) ...... 45 4.1 Data interpretation scheme for climate, lake levels, carbon and oxygen isotopic composition of carbonate, carbon and nitrogen isotopic composition of organic matter, and mineralogy for Al-Azraq AZ1 sediments. Modified from Hammarlund et al. (2005)...... 67

5.1 Photograph of Drive 2 section with white sediment matrix, and vertical brown veins between 3 and 4.5 meters ...... 70 5.2 High resolution photograph of carbonate varves from meters 13.75 to 14.30 in Al- Azraq Core AZ1. Picture taken at the Limnological Research Center (LRC), University of Minnesota, Minneapolis ...... 72 5.3 Photograph of variations in deposition at 21 m of Al-Azraq sediment core AZ1 ...... 74 5.4 Photograph and microscope (polarizing) image of fine carbonate grains in 1.06 m in the Al-Azraq sediment core AZ1 ...... 78 5.5 Photograph of carbonate grains occurring at 3.59 m in Al-Azraq sediment core AZ1. Cross polarized transmitted light ...... 79 5.6 Photographs of minerals identified in sediments of the Al-Azraq core AZ1 from 4.5 to 6 m: a-1. Hematite without polarizer, a-2. Hematite with polarizer, b. Quartz grain, c. Hematite, d. Ooid or nuclei of carbonate, and e. gypsum ...... 80 5.7 Photomicrographs of authigenic carbonate exposed to diagenesis and possible foraminifera fossils. Cross-polarized transmitted light ...... 81 5.8 Photomicrographs with non-polarized (top) and polarized light (bottom) of clear grains of authigenic carbonate present at 14.80 m ...... 82 5.9 Photographs of carbonate diagenesis grains at 23 m ...... 83 5.10 Photographs of centric and elongate diatoms identified as Stephnaodiscus sp. and Aulacoseira sp. at 35 m. Most of the diatoms are severely broken ...... 83 5.11 Polarized light photograph of grains of microcline and carbonate ...... 84 5.12 Diagram of clay, silt, and sand percentages from the grain size analysis of Al-Azraq core AZ1 ...... 85 5.13 Distribution of clay, silt, sand, and mean grain size of Al-Azraq core AZ1 ...... 86 5.14 Magnetic susceptibility graphs of four sections in the Al-Azraq core AZ1. a. rhythmites of carbonate at the end of 13m and beginning of 14 m; b. 32 cm

of the beginning of 21 m; c. and d. 45 m and 47 m, respectively ...... 89 5.15 Diagram of the geochemical data of Al-Azraq Core 1, including: %OC, %N, 13Corg, 15N, C/N ...... 91

5.16 Diagram of the geochemical data of Al-Azraq Core 1, including: %OC, %N, 13Corg, 15N, C/N ...... 95 5.17 Geochemical major elements including Al%, a%, Mg%, Na%, Fe%, and S% ...... 97 6.1 Clustering of major elements of Al-Azraq AZ1 core sediment identifies two major clusters. The second cluster contains two subgroups of major elements ...... 101

6.2 Clustering of trace elements of Al-Azraq AZ1 core sediment identifying one major cluster based on very low concentration levels and successive nesting clusters of increasing concentrations ...... 101

6.3 Clustering by depth of major and trace elements of the Al-Azraq AZ1. Group 1 represents higher moisture environments with three subgroups (1A, 1B, and 1C) reflecting lake phase, transitional phases and marsh environments. Group 2 (2A, 2B, 2C, and 2D) represents alluvial and eolian inputs of terrestrial materials to the basin and evaporative arid phases ...... 103 6.4 Clustering of stable isotope geochemistry of bulk organic matter of Al-Azraq AZ1. The clusters demonstrate close correlation between isotopic variables and support their use as proxies for determining sources of organic matter .....104

7.1 Diagram of the lithology of the Al-Azraq sediment core AZ1 and lithologic and climate zones 1-3 ...... 106

7.2 (a). Plot of Total Organic Nitrogen (%TON) vs. Percentage of Organic Carbon content (%OC) demonstrating the lack of inorganic nitrogen. (b). Plot of Total Organic Nitrogen (%TON) vs. Percentage of Organic Carbon content (%OC) without sample outlier (0.18, 4.36). Wile the R2 value decreases (R2= 0.1414), the slope intercept does not change, and therefore further demonstrates a lack diagenesis in Al-Azraq sediments ...... 108

13 7.3 Plot of the relationship between δ Corg and C/N ratios. It demonstrates low correlation between the ratios, indicating the absence of diagenesis of organic matter in AZ1 core sediments. Most of the organic matter falls within the range of aquatic algae with some mixing terrestrial plants. Two samples from the same zone fall within the range for C3 plants ...... 109 .

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13 18 7.4 Plot of δ Ccarb vs. δ Ocarb showing the none-effect of either methanogenesis, or the impact of sulfate reduction diagenesis of the carbonate calcium in Zone 1of the Al-Azraq core 1 ...... 111

7.5 SEM image of dolomite in Zone 1 of the Al-Azraq sediment core AZ1 (top). The EDS spectrum also shows Mg% and Ca% have similar peaks, also indicating the presence of dolomite ...... 112

7.6 Plots of Ca/Mg ratios vs. depth (a) and Mg% vs. Ca% (b) of the Al-Azraq sediment core AZ1. a. The dashed line shows the boundary of dolomite presence at 1.0, the red line maps fluctuation in the Ca/Mg ratio with depth; b. Mg% vs. Ca% indicating Zone 1 and Zone 3 have the most dolomite, but the clustering of Zone 2 samples near the intercept reflects the absence of dolomite in Zone 2 ...... 113

18 7.7 δ Ocarb vs. Mg (Mg+Ca) reflects a poor correlation between the chemical Data ...... 114

7.8 Fe/Al ratio, K/Na ratio, and Chemical Index Alteration (CIA) vs. depth of Al-Azraq core AZ1 exhibiting a signal indicative of detrital sources of iron in the upper core sediments of Zone 1, and a mix of authigenic and detrital source in Zone 2 ...... 116

7.9 Calcite and dolomite in the upper part of the core Zone 1, and ankerite Zone 2, and minor dolomite and carbonate diagenesis in Zone 3 ...... 118

7.10 Mg/Ca and Mn/Ca ratios indicating primary and secondary carbonate products for Zones 1, 2, and 3 of Al-Azraq core AZ1...... 119

18 7.11 δ Ocarb vs. Mg/(Mg+Ca) indicates the precipitated of carbonate in the Al-Azraq Basin from saline lake waters ...... 120

13 18 7.12 The covariance of δ Ccarb and δ Ocarb of calcium carbonate from the Al-Azraq Basin demonstrated that the basin has been a closed system throughout its history ...... 122

7.13 Carbon and oxygen isotopic composition of carbonate and grain size analysis identifying periods of dry and wet climate and low and high lake levels of Al-Azraq sediment core AZ1. Yellow zone represents eoline deposits as a result of wind activity. Blue zone reflects wet climate with increasing the precipitation, and light brown zone represents dry climate ...... 125

7.14 Mg/Ca ratio vs. oxygen isotopic composition of carbonates illustrating the

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source of carbonate in the Al-Azraq sediment core AZ1 in Zone1 ...... 126

7.15 Percentages of clay, silt, and sand from Zone 1c (a) and 1d (b). a. High percentages of sand over clay in Zone 1c support low lake level interpretation. b. In Zone 1d the reverse conditions with high percentages of clay over sand support interpretation of high lake level ...... 127

7.16 SEM image, and XRD and EDS spectra of the strontium sulfate mineral celestite from meter 4 of the Al-Azraq sediment core AZ1 ...... 128

7.17 Carbon and Nitrogen isotopic composition of bulk organic matter with results of grain size analysis. Show climate Zones 2a, 2b, 2c, 2d and Zones 3a and represent wet climate, whereas 3b reflect dry climate ...... 130

7.18 (a.) δ15N ‰ vs. δ13C ‰ and (b.) δ15N ‰ vs. C/N ratios illustrate different sources and types of vegetation in the Al-Azraq sediment core AZ1 ...... 133

7.19 SEM image, XRD pattern, and EDS spectra identify the presence of 3+ jarosite (KFe 3 (SO4) 2 (OH) 6), hydrous sulfate of potassium and iron in Zone 3a ...... 135

13 7.20 C/N ratios vs. δ Corg indicates the presence of diagenesis in Zone 3b of Al-Azraq sediment core AZ1 ...... 136

7.21 Comparison of SPECMAP stacked ocean δ18O‰ record (Imbrie et al., 1984) with AZ1 lithology, climate zones, and sediment chronology following the paleoclimate interpretations of Cordova et al. (2012) ...... 139

7.22 Comparison of δ18O records from Al-Azraq AZ1 (on the left) and Peqiin Cave speleothems (on the right) plotted against time (Bar-Matthew et al., 2003) and possible correlations following the paleoclimate interpretations of Torfstein et al. (2009) ...... 140

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List of Tables

Table Page

2.1 Natural abundance of H, C, N, O, and S ...... 11

5.1 Analytical methods and number of samples used in this fine resolution Project ...... 69

5.2 Important Ferromagnetic Minerals with Susceptibility Index ...... 87

ACKNOWLEDGEMENTS

Thanks to my adviser, Dr. Caroline Davies, for offering me this huge opportunity to work in the Al-Azraq basin in the end of 2005. It was the first time I left my country and went to Jordan. Also, I would like to thank her for offering assistance to bring me to the U.S. in order to further my education.

My thanks to Greg Cane, University of Kansas for all their assistance in offering the laboratory access for stable isotopes and geochemistry analyses in their labs.

I thank the committee members for their essential assistance with my geologic studies and readings and editings to my dissertation: Dr. Raymond Coveney, Dr. James Murowchick, and Dr. Nathan Oyler, and Dr. Kenneth Schmitz.

I thank the staff of the American Center of Oriental Research ACOR, Amman, Jordan who provided assistance while working with Dr. Davies in the Al-Azraq Basin.

I thank my parents who supported me during all my life by offering everything to further my education. Also, I must thank my uncles Dr. Riad Al-Ani and Dr. Hamed

Mahmood Al-Ani, and Mr. Kahtan Khalaf who always guide me to the right way in my life.

Moreover, they encouraged me to pursue the highest degree in my field. My thanks to my cousin Ahmad Mohammad for assistance with statistical analysis.

My thanks to my wife Amna Khalaf who always encourages me to finish my work on time and to be successful.

Finally, I thank everyone who helped me and I apologize if I failed to recall anyone who offered me help or support.

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I dedicate this work to

my father Ibrahim Ahmad and my uncles Dr. Riad Khaleel Al-Ani and Dr. Hamed Mahmood Al-Ani,

with love and affection.

All are special people in my life.

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CHAPTER 1

INTRODUCTION

Biogeochemistry as a modern field of study is newly applied to reconstructing past environments and climates. Biogeochemistry is rapidly expanding in the fields of geology and environmental science, as it reveals the complex processes between the multiple systems: geology, biology and chemistry. The concept of biogeochemistry is the exchange of chemical components between living organisms and the environment (Bashkin, 2002). Biota provide active principles in the biogeochemical cycles, meaning living organisms can modify global biological and geological activities and vice versa (Bashkin, 2002). Biogeochemical cycles play an important role in controlling climate; as elements such as carbon, nitrogen, sulfur and oxygen are involved in organic processes through photosynthesis, respiration and/or decay

(Mackenzie, 2009). Lacustrine sediments record biological changes over time and record the conditions of the environments of formation. Biogeochemistry examines organic and inorganic geochemistry identifying sedimentary processes and provide evidence for paleoenvironments and paleoclimate (Didyk et al., 1978).

Organic geochemistry is a useful tool for investigating paleoenvironment and paleoclimate processes. Organic matter accumulation in lake sediments provides information about the paleoenvironment that can be used to assess natural impacts of human processes in the local ecosystem (Meyers, 2003). Accumulation and composition of organic matter are influenced by the environmental changes and can be used to reconstruct past environmental conditions (Meyers and Ishiwatari, 1993; Killops and Killops, 1993). In general, organic matter in lake sediments includes a wide range of compounds, from simple compounds such

1 as methane to complex biopolymer molecules such as lignin and nucleic acids (Colman,

1996). The distribution and composition of lignin phenol provides three kinds of information relative to paleoenvironments: 1) climate change affects the presence of plants, 2) changes in the types of terrestrial plant remain in sediments indicate changing rainfall pattern, and 3) changes in relative proportions of vascular plants (land) to aquatic algae reflect sources of productivity (Orem and Kotra, 1997). Three important principles to consider in the application of organic geochemistry to paleoenvironmental reconstruction are: 1) Organic matter in lake sediments originates from biota that formerly inhabited the lake and/or its watershed, 2) the amount and composition of organic matter reveal the amounts and kinds of biota that lived in the past, 3) and isotopic composition preserved in organic matter provides information about environmental changes as indicated by vegetation changes.

Organic geochemistry data link biological processes from a broad range of environments (Schelske and Hodell, 1991; Bernasconi et al., 1997; Tenzer et al., 1999;

Routh et al., 2004). Primary production is identified by organic matter characteristics, trace elements, and carbon and nitrogen isotopic composition (Meyers and Lallier-Verges, 1999;

Boyle, 2001; Meyers, 2003). C/N ratio identifies the source of organic matter, e.g., is from aquatic or terrestrial sources (Meyers, 2003). The carbon isotopic composition is an indicator differentiating among C4, C3, and CAM plants (Meyers, 2003). Bulk organic matter and stable isotope geochemistry including carbon and nitrogen isotopic compositions indicate the paleoenvironment and paleoclimate.

Inorganic geochemistry is another tool used to characterize paleoenvironmental and paleohydrological processes. The presence and absence of major and trace elements serve as paleoindicator of environmental settings such as changing moisture conditions. For example

2 the presence and abundance of the elements K, Na, Mn, Ba, Sr, Al, and Ti identify mid-

Holocene climate changes in lacustrine sediments from Mengjin, Henan Province, China

(Dong et al., 2009). Another example uses specific combinations of major and trace elements in lake sediment to identify Holocene climate during the monsoon/arid transition zone from from the closed Lake Daihai in North China and at coastal Lake Taihu in the monsoonal area of the Yangtze delta, Eastern China (Sun et al., 2013). Geochemical studies of major and trace element compositions characterize Late Quaternary depositional environments and paleohydrological conditions in the paleolake San Felipe located in the western part of the

Sonoran Desert (Roy et al., 2010).

Geochemical studies of inorganic carbon and silicate, including carbon and oxygen isotopes, respectively, examine changes in climate over thousands of years (Leng and

Marshall, 2004). Particularly, the stable isotopes in carbonates are indicators of the paleohydrology and paleoenvironment (Leng and Marshall, 2004). Oxygen and carbon isotopic composition of carbonate in Lake Pergusa (Sicily, Southern Italy) demonstrated the changes in climate (Zanchetta el al., 2007). Oxygen isotopic values reflect temperature of carbonate precipitation which may differ for fresh water (Poulson and John, 2003).

Moreover, the carbon isotopic composition of carbonate reflects processes of gas exchange with the atmosphere, photosynthesis, respiration of the lake, and carbonate precipitation

(Talbot, 1990). In closed basin lakes, the precipitation (P)-Evaporation (E) ratio and residence time affect the oxygen isotopic composition (Talbot, 1990; Talbot and Kelts, 1990;

Lister et al., 1991).

Additional methods used in this project include grain size analysis, X-ray diffraction, and scanning electron microscopy (SEM) to support the paleoenvironmental and

3 paleohydrological interpretations. Grain size analysis identifies the distribution of sand, silt, and clay particles that reflects the energy environment of deposition. Stable isotope geochemistry and other proxies such as mean grain size contribute to lake level interpretations (Chang et al., 2008). X-ray diffraction and scanning electron microscopy

(SEM) provide the distribution of minerals in the Al-Azraq basin sediments. X-ray diffraction identifies the presence of minerals; whereas scanning electron microscopy demonstrates the properties of organic and inorganic materials at nanometer to micrometer scales (Goldstein et al., 2003).

The magnetic susceptibility of selected sections from the Al-Azraq core AZ1 provides distribution of ferric minerals in the sediments, which indicate the degree of erosion from the catchment (Sandgren et al., 1990 and McFadden et al., 2005).

The Al-Azraq Basin is located on the Jordan Plateau and is a very important source of water for the capital of Amman and surrounding cities comprising a majority of Jordan’s population. Analyses from previous work on Al-Azraq basin sediments from my master’s research (core AZ3) indicate the presence of organic matter throughout the lake sediments

(Ahmad, 2010). This makes the Al-Azraq basin sediment a good candidate for the application of organic geochemistry analysis. The scope of work for this research is high- resolution organic and inorganic geochemistry investigations of the Al-Azraq lake basin in the highlands of Jordan.

Al-Azraq sediment core AZ1, recovered from the basin in 1996, is located next to spring deposits. Cored sediments vary lithologically from one section to another. For example, the upper part of the core contains heavy carbonate deposition; whereas, in the middle of the core carbonate is absent but abundant diatoms are present, sometimes

4 dominating the sediment. The core was sampled into 520 samples; with sample intervals based on changes in the lithology. Smear slide analysis which gives a quick but detailed view of sediments was the basis for determining analytical methods.

Sediment core AZ1, consisting of sediment from the modern surface to 51 meters in depth, is the focus of this research. This research addresses the following questions. 1) What are the paleoenvironments of the Al-Azraq watershed through the mid to late Pleistocene as indicated by the distribution of organic matter in core AZ1, the types of organic matter present (terrestrial and/or aquatic plants), and changes in carbon isotopic composition of

13 organic matter (δ Corg)? 2) What are the paleohydrologic processes as reflected by major and trace elements in the cored sediments? 3) Do the oxygen and carbon isotopic composition of carbonates reflect the environmental conditions of the basin?

CHAPTER 2

BIOGECHEMISTRY APPLICATIONS

Biogeochemistry

Biogeochemistry is a field of study dealing with chemical, biological, and geological conditions and processes. Biogeochemistry integrates the biological processes of living organisms or their organic matter through chemical interaction with geologic, inorganic or non-living constituents. Biogeochemistry can be applied either on a small scale such as mud flat (Kristensen et al., 1985) or a large scale such as the entire Edisto River watershed, South

Carolina (McClelland et al., 1997). Biogeochemical cycles play an important role in the distribution of nutrients in the ecosystem and are sometimes referred to as nutrient cycles

(Schlesinger, 1996). Chemical reactions release energy and materials which flow through the processes of the ecosystem. Hence, biogeochemical study is an approach to understanding the flows of energy through chemical reactions and elements across an ecosystem. These energy flows leave distinct chemical signatures that can be process specific (Schlesinger,

1996). Identifying relict signatures enable the reconstruction of past environmental processes and conditions.

Carbon (C), hydrogen (H), nitrogen (N), oxygen (O), phosphorous (P), and sulfur (S) are the most important elements in the biogeochemistry cycles because they are involved in the production of animal and plant tissues (Schlesinger, 1996). Environments are controlled by the concentrations of these elements as either biotic or abiotic components. The elements are not only present in living or dead organic matter, but they also have the ability to accumulate in different biological and non-biological reservoirs (Bashkin, 2002).

Biogeochemical cycles, including carbon and nitrogen cycles, interact with the hydrogeological system in terrestrial and stream ecosystems (Lohse et al., 2009). Several factors control the presence of C and N in groundwater such as recharge rates, supply reactant, and depth and length of flow paths (Lohse et al., 2009). Hydrological and biogeochemical applications in the Central Valley, California identified connections between surface water, groundwater and uplands (Rains, in press). In Lake Tyrrell, Victoria,

Australia microbial activities drive the biogeochemical processes in both acidic and saline groundwaters (Hines, 1992).

These processes: photosynthesis and respiration, decomposition, the metabolism of nitrogen and sulfur, the inorganic nutrition of plants, and the weathering of rocks and soil are the interfaces between organisms and their environments. Using isotopic tracers biogeochemistry links these processes to changes in environment (Gorham, 1991). Moreover, biogeochemical cycles indicate human impacts on the environment such as acid rain, pollution, artificial fertilizers, and the greenhouse effect (Gorham, 1991).

In conclusion, biogeochemical cycles are important pathways to nutrient transfer, or moving elements from the environment into living organisms and back to the environment.

They are important for recycling materials, and without which life would be impossible.

Biogeochemistry is also an approach to understand the impact of humans on ecosystems. The cycles focus on elements essential for life such as carbon, nitrogen, sulfur, and phosphorous.

These elements cycle throughout the hydrosphere, lithosphere, atmosphere and biosphere.

Applications of Biogeochemistry for Paleoenvironments

The application of biogeochemistry to understand changes in past environments uses elemental pathways. Utilizing a variety of geochemical data such as isotopic composition

Choudharry et al. (2009) investigated changes in biogeochemistry records of Lake Nainital,

India, during the last 95 years. Records of environmental change are recorded in the geochemical data that can then be used to reconstitute the paleoenvironment and paleoecosystems (Schelske and Hodell, 1991; Bernasconi et al., 1997; Tenzer et al., 1999;

Routh et al., 2004). Biogeochemistry of ancient humans provided information about the history of human behavior and determines whether their diet included food from marine sources (Fogel et al., 1997).

Characteristics of organic matter reflect primary production changes (Meyers and

Lallier-Verges, 1999; Boyle, 2001; Meyers, 2003). Even though organic matter might be exposed to biological changes and anthropogenic activities, a small fraction of the organic matter can be useful to record and reconstruct geochemical data of the paleoenvironment in lake sediments (Meyers, 1994; Meyers et al., 1995). The source of organic matter can be identified in lacustrine sediments and indicates the type of biota (Choudharry et al., 2009).

The type of biota reflects biogeochemistry processes, trophic state shifts, and human activities in lacustrine sediment environments (Meyers, 1997; Tenzer et al., 1999; Meyers,

2003; Das et al., 2008; Routh et al., 2009; Choudhary et al., 2008).

Biogeochemical study also involves the field of archaeology. Using isotopic biogeochemistry provides information about modern and ancient of skeleton remains and their diets in the southern Asia, specifically in the Caspian Sea shore to the North and the southern part of the Arabian Peninsula (Bocherens et al., 2000). Biogeochemistry combined

8 with archaeology and bioarchaeology provide information about migration patterns in the

Tiwanaku polity, Western Bolivia, (ca. ad 500–1000) (Knudson, 2001). Constructing human immigration and mobility patterns uses the application of strontium isotope records (Bentley,

2006).

Biogeochemistry of ocean sediments is also a good indicator of the history of past environments. Marine sediments and sedimentation rate provide information about changes in past environment in the Late Cenozoic and Cretaceous age (Stein, 1990). The emission of methane from marine sediments and in the atmosphere is controlled by anaerobic methane oxidation; this in turn impacts the global methane budget (Alperin and Reeburgh, 1985;

Reeburgh, 1989). In the Aarhus Bay, Denmark, subsurface marine sediment contained an anaerobic methane oxidation zone (Thomsen et al., 2001). The presence of major and trace elements in marine sediments also reflects the redox conditions at the bottom of the water column during time of deposition (Calvert and Perderson, 1993). The organic matter of biomarkers are preserved in marine sediments and record information about past environments (Pancost and Boot, 2004).

In summary, biogeochemistry provides information about the origin of organic matter and biogeochemical processes in marine sediments. These reflect well the paleoenvironments and paleoclimate forming the marine sediments. Biogeochemistry also identifies the redox zone in marine sediment, which in addition to the anaerobic methane oxidation, affects the global change.

Stable Isotope Geochemistry

Stable isotope geochemistry is the modern techniques that can be applied to understand the history of the Earth. This section gives brief description about isotopes and their theory. Most the information is from Sharp (2007).

Isotopes Definition and Notation

Stable isotopes have a wide range of applications including the field of geology. The nucleus of an atom contains a number of protons (Z) and a number of neutrons (N) (Hodgson et al., 1997). In other words, the simplest definition of isotope is atoms composed of protons, electrons and neutrons. Isotope of the same elements differs from one another by the number of neutrons in its nucleus. For example, oxygen has three natural isotopes 16O, 17O, and 18O with 8 protons and 8 neutrons, 8 protons and 9 neutrons, and 8 protons and 10 neutrons, respectively. Carbon also has three natural isotopes 12C, 13C, and 14C.

The isotopic composition of elements with low atomic numbers depends on the origin of the element compounds (Faure, 1991). Most isotopes examining the earth history are carbon (C), hydrogen (H), nitrogen (N), oxygen (O), and sulfur (S) because they are abundant elements in the earth's crust, and they are present as solid, liquid, and gas in the atmosphere, lithosphere, and hydrosphere (Faure, 1991). In addition, these elements are involved in tissues of living organisms (Sharp, 2007). The stable isotopes ratios of five elements have been written as have heavy isotopes (rare) to light isotopes (abundant). Even- even isotopes are more abundant than odd-odd isotopes (Table 2.1).

Table 2.1. Natural abundance of H, C, N, O, and S.

Natural Nuclear Isotope Mass Abundance Z N Spin (I) Atoms (%) 1H 1.007 99.989% 0.001% 1/2 0 2H 2.014 0.012% 0.007% 1 1 1 100.000% 12C 12 98.93% 0.08% 0 6 13C 13.003 1.07% 0.08% 1/2 6 7 14C 14.003 100.00% 0 8 14N 14.003 99.63% 0.01% 1 7 15N 15.000 0.37% 0.01% ½ 7 8 100.00% 16O 15.994 99.757% 0.02% 0 8 17O 16.999 0.038% 0.001% 5/2 8 9 18O 17.999 0.205% 0.01% 0 10 100.00% 32S 31.972 94.93% 0.31% 0 16 33S 32.971 0.76% 0.02% 3/2 17 34S 33.967 4.29% 0.28% 0 16 18 36S 35.967 0.02% 0.01% 3/2 19 100.00%

Isotopes are measured as a ratio between the two isotopes of a given elements (X):

EQ1.

Where F is the concentration of an isotope of elements X. is considered the most abundant. The notation for isotopic fractionation states conventionally that δX (Clark and

Fritz 1997; Criss, 1999) is:

EQ2.

R reflects the isotope ratio of X elements. δ is the notation of the change in fraction isotope of given elements and is conventionally presented in parts per thousand (‰).

Fractionation of Isotopes

Isotopic fractionation is the differential enrichment of one isotope relative to another due to preferences in physical (e.g. evaporation), chemical (e.g. precipitation), and biological processes. This selectivity is expressed by the ratios of relative abundances of the light and heavy isotopes. The isotopic composition of certain elements depends upon the differences in isotope masses, temperature in which the compound occurs, and the character of element form (Faure, 1991). The electronic structure of molecules is responsible for chemical reactions. Minor mass differences between molecular species of different isotope records different rates. Therefore, this will occur in mass dependent where product will be either enriched or depletion relative to starting matter. Hence, lighter molecules have a greater opportunity to be present in the chemical reactions, but the heavy molecules connect with strong bonds (Clark and Fritz, 1997; Criss, 1999). Isotopic fractionation is divided into two processes: equilibrium fractionation and kinetic fractionation.

Chemical equilibrium happens when products and reactants have steady state and do not change through the time of reaction. In other words, the isotopic composition of both reactants and products will be constant. Temperature represents equilibrium time and equilibrium position (Clark and Fritz, 1997). The fractionation at high temperature disappears and the fractionation at low temperature reveals large differences between products and reactants (Criss, 1999).

Based on this relationship, it is easy to estimate a temperature of formation such as two minerals or water with precipitation (biogenic carbonate) (Sharp, 2007). In addition, the application of temperature fractionation creates the applications of isotopes links chemistry

12 and geology such as oxygen isotope paleotemperature (Urey, 1948, Epstein et al., 1951), carbon, hydrogen, nitrogen and sulfur isotopes (Sharp, 2007).

Kinetic fractionation takes place when a chemical reaction moves away from equilibrium as a consequence of changes in temperature, adding or removal reactants or products from reaction that leads to be away from equilibrium condition (Clark and Fritz,

1997). It happens in both nature and laboratory (Sharp, 2007; Clark and Fritz, 1997). It is associated with processes such as evaporation, diffusion, dissociated reactions, biological processes (Sharp, 2007). A good example of kinetic fractionation is the evaporation process of water. In this process, with the application of energy the water molecular transfers from liquid phase to water vapor and then from vapor phase back to water phase (condensation). In this situation, equilibrium is only achieved in humidity or when there is no evaporation

(Criss, 1997). Another good example of kinetic fractionation is uptake by biological processes (Sharp, 2007). Organisms utilize preferentially light isotopes due to lower energy produced by the fractionation between heavy isotopes and light isotopes. The energy of bonds and reaction pathway uses are important in this fractionation. The greatest isotopic fractionation occurs in slower reactions than faster reactions due to the greater organisms for the time to be selective.

Applications of Isotope Geochemistry for Paleoenvironment and Paleoclimate

Reconstructions

Organic Matter in Lake Sediments

Lake environments consist of a body of water that holds diversities of life including different organisms. Several factors control lake diversity such as size, biological activities,

13 watershed types, bottom morphology, and other limnological factors (Meyers and Ishiwatari,

1993). Even though organic matter is a minor constituent, it is important in lake sediments because 1.0 % of organic matter in lake sediments is adequate to identify the source of organic matter (Meyers, 1993). Lake sediments hold valuable information about the source of organic matter that either from the lake itself or comes from the surroundings area (Meyers,

2003) (Figure 2.1). Different organisms that lived in lake were able to produce a variety of organic matter such as protein, lipid, carbohydrate, and other biochemical nutrient. Organic geochemistry examines organic matter preserved for millions of years in lacustrine sediments providing information about the lake environmental history (Meyers, 2003). Geochemical oxidation process impacts the organic matter which makes it more dynamic in sediments

(Meyers and Ishiwatari, 1993). Preserved organic matter in lake sediments provides information about human activates during the lake period (Meyers, 2003). More details and examples about using organic matter in lake sediments as an indicator of paleoclimate and paleoenvironment are described in Meyers and Ishiwatari (1993); Meyers (1997); Dean

(1999); Meyers and Lallier-Verges (1999); and Meyers and Teranes (2001).

CO2 C3 plants -21 to -35‰ 13C O2 C4 plants -9 to -20‰ 13C 12C

OM preserved in 13C basin sediments

15N

16 O 18 algae -10 to -22‰ 13C O 13 CO2 plankton -20 to -21‰ C O2

Figure 2.1. The relationship of oxygen and carbon isotopes ranges to C3 and C4 plants, and isotopes commonly preserved in lake sediments.

Organic matter in lacustrine sediments originates from several different sources.

There are three sources of organic matter. Primary sources are aquatic algae, which lack cellulose in their structures, and terrestrial plants. In addition, secondary sources of organic matter are from either bacteria or microbes. Two kinds of terrestrial plants are: 1) plants lacking woody and cellulosic tissues; and 2) plants with tissues such as grasses, shrubs, and trees (Meyers and Ishiwatari, 1993). Aquatic plants such as algae also lack cellulose in their structures. Organic matter from bacteria and microbes does add not additional organic carbon into the lacustrine sediments. However, microbes break down organic matter residue

15 produced either on land or in the water body through biosynthesis, and produce characteristic biomarkers (Meyers and Ishiwatari, 1993) (Figure 2.2).

Figure 2.2. Processes of organic matter production in lake sediments, and involving delivery of organic matter to sediments. Modified from Meyers and Ishiwatari (1993).

Isotopes of Carbon and Nitrogen and C/N ratio in Lacustrine Sediments

13 The carbon isotopic composition of organic matter (δ Corg) in lake sediment is a very vital proxy for understanding the source of organic matter, paleoproductivity, and to identify the changes in the nutrients in surface water (Meyers and Teranes, 2001). 13C/12C reflects the

13 presence and improvement of aquatic algae (Brenner et al., 1999). δ Corg values act as tracers for past changes in land plants and aquatic algae (Leng, 2006). Algae (C3 plants) use

12C to evolve organic matter with an average 20‰ lighter than the δ13C of dissolved inorganic carbon (DIC) (O’Leary, 1989). As a consequence, the organic matter eliminates

12 13 C and the remaining of DIC is rich in δ C of the new organic matter (Meyers and Teranes,

2001; Sharp, 2007).

Figure 2.3 gives an example of isotopic fractionations of different organic matter types. If lake water flows through an area dominate in C4 plant, then the carbon isotopic

13 composition of total dissolve inorganic carbon (δ CTDIC) will be high. Moreover, it gives high values where the lake water is in the stratified zone, such as in the beginning of an anoxic zone where organic matter oxidizes preserving with high amount of organic matter by removing 12C from the system. During high organic matter in the lake, especially, if the

13 12 organic matter in lake mixed with terrestrial organic matter, δ CTDIC values will lower as C

13 liberates. However, methane formation gives a signature greater than +2.5‰ of δ CTDIC

(Rau, 1978; Coleman and Fry, 1991; Keeley and Sandquist, 1992; Meyers and Teranes,

2001).

Figure 2.3. Organic matter production in lake sediments and carbon isotopic signature of each kind of organic matter in lake freshwater. Modified from Leng and Marshall (2004).

Nitrogen isotopic composition is another proxy that is a useful in identifying the source of organic matter even though it is not widely utilized in paleolimnology (Herczeg et

17 al., 2001). It is considered a good indicator of paleoproductivity and past availability of nitrogen to aquatic primary producers (Meyers and Teranes, 2001) However, nitrogen is used less in lacustrine isotope studies than carbon isotopic composition due the complex of dynamic of biogeochemical cycles (Leng, 2006). The difference in N15/N14 ratios between inorganic nitrogen reservoir available to plants in water and plants in land are found in the nitrogen isotopic composition (δ15N) (Meyers, 2003). The difference between 15N/14N ratios of inorganic nitrogen of plants in water to those on land indicates the source of organic matter (Meyers, 2003). Aquatic algae utilize dissolved inorganic nitrogen (DIN) in the form

- of NO 3, whereas, plants use atmospheric N2 (Peters et al., 1978). Figure 2.4 illustrates the idealized nitrogen isotopes cycle in a small stratified lake.

Figure 2.4. Nitrogen isotopic composition of fresh water. Modified from Leng and Marshall (2004).

Carbon and nitrogen isotopic compositions and C/N ratio are good indicators of the source of organic matter in different environments such as estuary, ocean, and lake sediments

(Altabet, 1988; Matson and Brinson, 1990; Thornton and McManus, 1994; Cifuentes et al.,

1996; Nakatsuka et al., 1997; Goñi et al., 1998; Graham et al., 2001). In addition, primary productivity and pCO2 in the atmosphere are identified by the carbon isotopic composition of organic matter (Hollander and McKenzie, 1991; Schelske and Hodell, 1991; Fontugne and

Calvert, 1992; Meyers, 1997; Brenner et al., 1999). Moreover, nitrogen isotopic values

(δ15N) reflect nitrate utilization by aquatic (Calvert et al., 1992; Altabet and Francois, 1994;

15 Teranes and Bernasconi, 2000) and N2 fixation by plants (Haug et al., 1998). δ N reflects the paleoproductivity of organic matter lacustrine sediments (Meyers and Teranes, 2001).

Paleo-primary productivity of Lake Ontario was determined by the carbon and nitrogen isotopic compositions (McFadden et al., 2004). Taipei Basin, northern Taiwan, had the opportunity to be investigated from the source of organic matter utilizing δ13C, δ15N and C/N ratio. The values identified an arid period during marine isotope stage 2 (MIS2) and mid MIS

6, whereas during MSI 1 fluctuations reflect variations in aquatic productivity (Ku et al.,

2007).

CO2 in the atmosphere can be estimated from the carbon isotopic composition of land plant tissue (Arens et al., 2000). Measurement of δ13C land plants identified quantitative shift in isotopic composition of atmospheric CO2 (Faure et al., 1995; Groke et al., 1999).

Moreover, carbon isotopic composition of atmospheric CO2 correlates marine and terrestrial rocks producing chemostatigraphy of the global carbon record (Koch et al., 1992; Turney et al., 1997; Groke, 1998).

Oxygen and carbon isotopes are commonly preserved in lake sediments and reflect the proportion of C3 and C4 plants through their representation of isotopes ranges. The δ13C values provide further evidence of the proportion of C3 to C4 plants (Cotton et al., 2012).

Isotope geochemistry of Empakai Crater lake sediments record climate change in northern

Tanzania. The data records the variation in organic matter sources throughout the lake sediments with more humid period distinguished by the presence of phytoplankton and C3 land plants (Muzuka et al., 2004). The δ13C of sediment organic matter from the northern

Gulf of Mexico indicates change in vegetation type from C4 tundra grasses to C3 woody plants (Meyers, 1994). Carbon isotopic composition identifies the distribution of organic matter as being 50% from three lakes (Lakes Makat, Ndutu, and Masek) in Tanzania. Also, throughout the cores the distribution of C3 to C4 plants, with the low values of δ13C indicating an abundance of C3 plants (Muzuka, 2006).

Carbon and Oxygen Isotopes of Carbonate

Carbonate in salt lake sediments

Properties, kinetic energy, chemistry, and productivity of water from lacustrine environments differ quintessentially from the characteristics of marine environments. Lakes sediments are more strongly subject to long and short-term modification by changes in climate, water chemistry and lithology of sediments.

Lacustrine carbonate precipitation differs by the salinities of different lake types such as: fresh water, salt water, and Playa lakes. Terrestrial carbonate redeposit in lake sediments occurs either close the shoreline or within the lake itself (Flugel, 2010).

Lakes have exorheic (open-basin) or endorheic (closed-basin) drainage. This section focuses on the formation of carbonate only in closed-basin lakes because the saline paleolake of the study area is a closed-basin lake. Closed-basin lakes dominate in arid and semi-arid environments. Climate change is most likely to turn freshwater

20 lakes to saline such as the Great Salt Lake, Utah, and the great lakes in the East

African rift system (Flugel, 2010).

Evaporation and precipitation are the dominant processes in saline of lakes. If evaporation is equal to precipitation, it is a perennial lake that maintains open water throughout the year. However, when evaporation exceeds precipitation, salinity and

Mg/Ca increase with the depletion in Ca concentration (Flugel, 2010). Mono Lake,

Death Valley, California, Great Salt Lake, Utah (Eardly, 1966; Halley, 1976), and

Solar Lake, Israel (Krumbein and Cohen, 1974; Friedman 1978) are case studies of closed-basin lakes characterized by high evaporation and concomitant depletion of

Ca.

Carbonate in salt lakes appears in many different forms (Flugel, 2010). 1.)

High-Mg calcite and aragonite precipitation characterizes the Dead Sea, or Low-Mg calcite and High-Mg calcite due to an increase in the ratio of Mg/Ca characterizes

Lake Balaton, Hungary. These two kinds of calcite: Low-Mg calcite and High-Mg calcite substitute Mg2+ for Ca2+, have Mg percentages less than 4% and greater than

11-19%, respectively (Nichols, 2009). 2.) Fine laminations of carbonate containing

Ca-Mg carbonate, detrital quartz, silicate and organic layers. 3.) Ooid sands form in nearshore, shallow water. Sometimes these deposits are associated with algal bioherms and varves of micritic aragonite. 4.) Pisiod and carbonate encrustations form as a result of losing CO2 by degassing. Also, photosynthesis in spring water on the playa surface leaves behind a supersaturation of calcite (Risacher and Eugster,

1979). 5.) In lake bottom, waters hydrothermal fluids produce thin layers of aragonite

21 and magnesium such as at Lake Tanganyika, and lakes in East-Central Africa (Cohen and Thouin, 1987; Stoffers and Botz, 1994).

Oxygen and Carbon Isotopic Compositions of Lacustrine Sediments

Carbonate lake sediments contain primary minerals that precipitate within the lake. These minerals are present either as authigenic or biogenic minerals, while detrital minerals are allochthonous, or produced outside the basin, as a result of weathering from the catchment of the lake (Leng, 2006). Photosynthesis by algae and macrophyte precipitates calcite. In addition, ostracods, mollusca shells, and diatoms are also biogenic sources of calcite (Leng, 2006). Carbonate in lakes appears in a variety of forms such as bulk carbonate (marl, mollusca, ostracods, and detrital carbonate), and carbonate minerals (calcite, aragonite, and dolomite) (Leng, 2006). In order to use isotopes of carbon or oxygen from carbonate, authigenic and biogenic sources of carbonates have different isotopic fractionation and must be separated from each other (Friedman and O’Neil, 1977; Rosenbaum and Sheppard, 1986; Leng and Marshal, 2004). However, it is very difficult to separate detrital minerals from other carbonate or authigenic minerals.

Oxygen Isotopes Fractionation in Inorganic Carbonate

Oxygen isotopic composition of lacustrine carbonate provides information about changes in either temperature or the isotopic composition of lake water. These changes might be due to the climate changes either in temperature such as changes in precipitation/evaporation or changes in the source of lake water (Leng, 2006).

Oxygen isotopic composition of authigenic minerals such as carbonate in lakes reflects changes in paleotemperature (Buchardt and Fritz, 1980; Siegenthaler and

Eicher, 1986; Ito, 2001; Schwalb and Dean, 2002; Leng and Marshall, 2004).

The following are several factors impacting the oxygen isotope of lacustrine

18 carbonate (δ Ocarb) (Figure 2.5). Temperature and isotopic composition of lake water

18 are the first factors that affect the δ Ocarb if the precipitation of carbonate is in isotopic equilibrium. Local changes in microenvironment or rate of precipitation are responsible for the vital effects in biogenic carbonate precipitation that offsets the

18 δ Ocarb signal. Knowing environmental characteristics and time of carbonate

18 18 precipitation are important for interpreting temperature from δ Ocarb. δ O of lake

18 water is influenced by evaporation rates thereby affecting the δ Ocarb (Leng and

Marshall, 2004).

13 18 Oxygen and carbon isotopic composition of carbonate (δ Ccarb and δ Ocarb) provide information about paleoenvironment, paleohydrology, and paleoclimate

(Talbot, 1990; Talbot and Kelts, 1990; Rosen et al., 1995; Alonso-Zarza, 2003;

Liutkus and Wright, 2008; Deocampo, 2010). δ18O and δ13C demonstrate significant temperature and humidity signals from carbonate nodules in sediments of the Ganga

Plain (Rahaman et al., 2011). Oxygen isotopes of lacustrine authigenic carbonate from Lake Tianshuihai in western Qinghai-Tibet Plateau, China, indicated changes in moisture sources due to the uplift of Qinghai-Tibet Plateau at 130000 (Houyun and

Zhaoyu, 2002).

Figure 2.5. Factors impacting the oxygen isotopic composition of carbonate. Modified from Leng and Marshall (2004).

Analysis of the oxygen and carbon isotopic composition of paleosol carbonate from the western margin of the Olduvai Basin, Tanzania indicates an increase and decrease in local precipitation. However, the carbon isotopic composition values of bulk organic matter reflect a variety of C4 plants ranging from 40-60‰ (Sikes and

Ashley, 2007). The temperature and salinity of lake water can be determined by oxygen isotopic composition of autochthonous carbonate (Chang et al., 2008). Low averages of oxygen isotopic composition (-5.5‰) from carbonate in paleo–Lake

Olduvai, Tanzania, indicate a wet period. Whereas, low averages of carbon isotopic composition (-4.1‰) indicate limited atmospheric exchange, high plant decay, and/or increased groundwater flow (Liutkus et al., 2005). Oxygen and carbon isotopic compositions of carbonate from a paleolake in the central Himalaya distinguished alternating periods of wet and dry climate (Wang et al., 2012).

In addition to autochthonous carbonate, oxygen and carbon isotopic compositions of biogenic carbonate from organisms such as ostracods reveal information about past water temperature and lake productivity. δ13C and δ18O of crystal carbonate and ostracods increased and decreased, respectively indicating the presence of organic matter, DIC input, and water residence time. Also the values of both proxies revealed that the lake level was initially low and increased over time

(Pueyo et al., 2011). Oxygen and carbon isotopic compositions of calcite from ostracods and aragonite gastropod shells from a Middle Miocene lake in the

Steinheim Basin, SW Germany, determined variations in lake level, water chemistry, and temperature. Both values indicated similarly more positive values than marine carbonate. δ13C values of biogenic carbonate equate to fluctuation in paleolake level, while δ18O values indicated short-term differences between meteoric water and long term of evaporation (Tütken et al., 2006).

In addition to paleolenvironment and paleoclimate reconstruction, oxygen and carbon isotopic compositions provide information about paleohydrological conditions. δ18O and δ13C of carbonate reflects the paleohydrology of the Ramlat as-

Sab’atayn (Southern Arabia). The increase in δ18O indicates the presence of Typha, while the decrease in δ13C represents strong evaporation during low lake levels

(Le´zine et al., 1998). Again, oxygen and carbon isotopic compositions indicate the lake paleohydrology of non-marine deposition from Upper Aptian lacustrine carbonate in northeastern Brazil (Paz and Rossetti, 2006). Geothermal flow, volcanic

13 CO2, and degassing during groundwater discharge are mechanisms that enrich C

25 values in a shallow lake in the Andean Altiplano, South America (Schwalb et al.,

1999; Valero-Garcés et al., 1999, 2000; Gibert et al., 2008).

The fluctuation of oxygen and carbon isotopic compositions from Bear Lake indicates oscillation between closed and open basin conditions. This oscillation could potentially be in response to increased atmospheric moisture or input from Bear River

(Bright, 2006). Oxygen and carbon isotopic compositions of carbonate demonstrate the paleohydrological evolution of Lake El Peinado, southern most Altiplano. In addition, the sedimentological proxy of grain size indicates a decrease in lake level might correspond to the Little Ice Age (Valero-Garcés, 2000). Lake Uinta, southwestern Uinta Basin, Utah responds hydrologically to local and distal tectonic forcing identified by O, C, Sr, isotopes of lacustrine carbonate in addition to Sr/Ca

13 18 ratio (Davis et al., 2008). δ Ccarb and δ Ocarb signify that Lake Qinghai is a closed

13 18 basin based on the covariance between δ Ccarb and δ Ocarb (Xu, 2006).

CHAPTER 3

STUDY AREA AND BACKGROUND RESEARCH

Introduction

Jordan is located in southwest Asia. It is bounded by Syria in the north, Iraq to the east, Saudi Arabia to the east and southeast, and Israel in the west. The Jordan

Plateau is located from 35°30’W-37°30’E latitude to 32°00’N -29°30’ longitude with elevations ranging from 1734 m at the escarpment of the western plateau and between 850 to 500 meters above sea level in the Playa lakes of the eastern desert

(Figure 3.1). The Jordan Plateau is bounded by the Jordan-Dead Sea Rift Valley to the west, which is a small extension of the East African Rift System. The plateau is the divide between two drainages: one flowing west down steep wadis into the Dead

Sea, and the other flowing east into the desert interior (Burdon, 1959; 1982). Jordan land cover is approximately 40% playa lakes. The modern climate on the Jordan plateau is semi-arid to arid. However, in the past the climate was more moist than the present as indicated by the presence of numerous of playa lakes across the plateau.

The Al-Azraq Basin is the second largest basin on the Jordan Plateau after the Al-Jafr Basin. The Al-Azraq contains one of the countries two fossil aquifers, making the basin of vital importance to the capital city of Amman and surrounding cities as a major source of drinking water. Today the basin receives less than 50 mm of precipitation during the winter months, whereas the Al-Azraq Oasis, on the

27 western margin of the Al-Azraq playa has limited subsurface springs. The basin was formed by a sequence of tectonic and faulting events (Ibrahim, 1996).

Figure 3.1. Map and Google image of the area of study in Al-Azraq Basin. Location of sediment cores AZ1 and AZ3 within the Qa Al-Azraq.

The Jordan Plateau experienced two major geologic events: tectonic shifting and up-warping of the Nubian Arabian Shield along the Dead Sea and Rift Valley.

The other event was multiple transgressions and regressions of the Tethys Sea in the

Miocene (Bender, 1975). The result of the former was outcropping of the uplifted plateau in the southwest of the Jordan due to dipping of the shield margin to the east

28 and southeast (Powell, 1989; Moh’d, 1986); and the later resulted in thick biogenic sedimentation across the plateau.

Jordan’s climate today is arid to semi-arid with the highest precipitation along the Jordan Plateau and the areas to the east are in a rainshadow created by the western escarpment (Figure 3.2). The only basin with standing water year round

(when not over pumped) due to several subsurface springs is the Al-Azraq Basin. It is one of only two fossil aquifers and one of the main sources of water for the capital

Amman and its surrounding cities (Committee on Sustainable Water Supplies in the

Middle East, 1999). During the summer time, the weather is dry and hot, whereas winter weather is cold with more precipitation supporting an ephemeral basin in the

Al-Azraq.

The presence of ancient lakes across the plateau indicates increased moisture during the Pleistocene (Abed et al., 2008; Davies, 2005a; Shahbaz and Sunna, 2000).

Even though the present climate is dry, in the past the climate was more moist as reflected by the presence of the Al-Azraq basin.

Geological Setting and Surficial Geology

Distribution of Regional Tectonic and Geological Units

The location of geological structures in Jordan is based on its position at the juncture of three tectonic plates: the African, Arabian, and Levantine plates.

Tectonic activities during the Precambrian formed the crystalline basement rocks of

Jordan (Bender, 1974). A north-south graben formed during the beginning of

Miocene separates the Arabian and Levantine Plates, represented now by the Jordan

River, the Dead Sea, and the Wadi Araba (Meissner, 1986).

Figure 3.2. Isohyet map of mean annual precipitation in millimeters (mm). The highest precipitation is along the escarpment of the Jordan Plateau. Modified from Water for the Future, NAP (1999). Data sources from information in Salameh and Bannayan (1993) and U.S. Central Intelligence Agency (1993).

Faults parallel to the down-thrown block of the graben caused movements during the post-Miocene (Garfunckel, 1997). Most of these faults are strike-slip. However, most recent movements reflect by normal faulting (Neev and Emery, 1995).

Transform faults present in the Jordan Plateau are perpendicular to the Rift

Valley Fault (Cordova, 2007). These faults control the major drainage networks on the western slope of the plateau draining into the Rift Valley (Beheiry, 1968-69; Al-

Hunjul, 1995; and Shawabekeh, 1998). From north to south the major fault based wadis draining into the Rift Valley are: Wadi Ziqlab, Wadi Zarqa, Wadi Karak,

Wadi Mujib, Wadi El Hasa, and Wadi Dana. Moreover, these faults play an important role in the volcanic activities forming basalt in Karak Plateau and Wadi

Zerqa (Bender, 1974; Steinitz and Bartov, 1992). Most relevant to the study are the faults responsible for the formation of two most important basins in the Jordan

Plateau, the Al-Azraq and the Al-Jafr Basins (Beheiry, 1968-69; Bender, 1974).

Following Bender (1974), Powell (1989), and Cordova (2007) the basic geological units of Jordan are divided into somewhat unconventional units. The first and oldest unit is Precambrian and is exposed at the base of the Plateau in the southern of Wadi Araba and areas around Aqaba. The most important rocks in this unit are granite, granodiorite, and porphyry in addition to some metamorphic rocks such as gneiss. The second unit is a sandstone formation with exposures in the south of the country along the Rift Valley escarpment in the area of Wadi Ram and Petra.

It is divided into two major groups: the Ram and Kurnub. This unit represents

Paleozoic and Triassic-Jurassic periods, respectively. The third unit representing the

Upper Cretaceous and Eocene periods is sedimentary including marine rocks such as limestone in addition to marls, travertine, and phosphorites. These are exposed in the

Central Plateau and Western Highlands. Finally, the youngest unit exposed in the

Figure 3.3. Diagram showing the three tectonic plates and the distribution of regional faults in Jordan Plateau. Modified from Natural Resources Authority, Amman, Jordan

Badia region in the north of the country belongs to the Plio-Pleistocene Period.

During the Tertiary age most accumulation in the Rift Valley is terrestrial detrital sediments dominated by conglomerate and breccia such as the Miocene

Conglomerate in Wadi Dana.

Mineral Deposits Distribution

This section will discuss the distribution of minerals in Jordan. The most abundant mineral deposits are limestone, dolomite, feldspar, and gypsum. Mineral exploration and mapping is conducted and published by the Natural Resources

Authority of Jordan.

The most important sedimentary rocks occurring in Jordan are limestone.

Pure limestone appears with 93% CaCO3, with some impurities such as marl and silica, which formed from the accumulation of detrital shells. The main location of pure limestone is in the central part of Jordan from Siwaqa to Jurf Ed-Darawish in addition to two other locations in the east and northeast of the country (Figure 3.4).

Another sedimentary rock is dolomite (CaMg (CO3) 2). It represents different ages and occurs in different areas of Jordan associated with limestone in the area between

Wadi Isal and Wadi Ahemir Iasal, Ghour Al-Haditheh, Ein Lahtha, Al-Ena, and Ras

En Naqab (Yager, 2000) (Figure 3.4).

Feldspar is another silicate mineral occurring in Jordan. Alkali granite rocks, leucogranite, feldspar pegmatites, and alkali-rich granite are responsible for forming medium and coarse grained feldspar deposits in Jordan. Feldspar depositions appear in Jordan in the area of Aqaba, especially in Al-Jaishieh, Wadi Sader Mulghan, and

Ayn Al Hashim (Shakkour et al., 2006) (Figure 3.4).

Another important mineral is gypsum. When a solution is saturated with

2- 2+ SO and Ca ions, gypsum (CaSO 2H O) forms by precipitation. In general, 4 4 2 gypsum occurs in different forms such as gypsite, massive gypsum, satin spar

(fibrous), and selenite. The eastern part of Jordan is the main area where gypsum

(Gypsite or Gypcrete) appears, especially in the Al-Azraq area to the Zarqa River

Area, Jabal Bani Hameda, Wadi Al-Mujib, Wadi Ibn Hammad, and Wadi Al Dahel

(Tarawneh et al., 2006) (Figure 3.4).

Clay minerals are important deposits in Jordan. The most common clay minerals found in Jordan are kaolinite, illite, and smectite (Abed et al., 2008).

Kaolinite is hydrous aluminum silicate (Al2Si2O5(OH)4) containing 23.5% alumina,

46.5% silica, and 14% water. It is useful in a variety of industrial processes such as ceramics and filling and coating paper. The properties of the clay deposits in Jabal

Umm Sahm indicate the deposit kaolinite with the standard specification of the ceramics industry (Al-Momani, 2000). Also, the study of clay deposits in Jordan indicates that the deposit of the source of aluminum is useful of using in ceramic industry (Bayook, 1992). In 2000, Geoindustria, a Czech Company, identified the locations of kaolinite in Jordan as in Batn el-Ghoul, Al-Mudawwara and Jabal Umm

Sahm and Dubaydib (Yasin, 2006; Yager, 2000) (Figure 3.4). These areas were determined to be industrially positive.

Silica sand minerals dominate in Jordan with almost pure sands occurring in

Ras En Naqab with 99.31% of SiO2 and 0.03% of Fe2O3 (Yager, 2000). Fine-grained crystalline silica of tripoli used commercially as an abrasive is found in the Karak

District. Other localities of the silica sands are Qa’a Disi, Petra and Ein El Badia,

Al Jayoshia, and the Wadi Es Siq-Wadi Rakiya (Madanat, 2006) (Figure 3.4). Other mineral is sulfur and appears in the oil shales ranging from 4% to 5% (Yager, 2000).

Figure 3.4 Mineral distributions in Jordan. Modified from Natural Resources Authority, Amman, Jordan.

Al-Azraq Basin Overview and Description

Introduction

Basin is located 75 km east of Amman. It is an (األزر ق :Al-Azraq (Arabic elongated basin, 50 km2 by 30 km2 and is considered a hydrologically closed basin.

The elevation of the basin is low in the central mudflat at 500 meters above sea

35 level. Faults present in the Al-Azraq Basin area include the Siwaqa Fault north of the

Qa area and the Fuluq Fault south of the Qa area (Ibrahim, 1996). Al-Harra volcanic field surrounds the basin in the northwest extending to the North Arabian Volcanic

Province covering 11,000 km2 within northeastern Jordan (Bender, 1974). These days the Al-Azraq Basin covers several areas such as the springs, freshwater pool, marshes and a crescent-shaped mudflat. During high precipitation in Jordan, the basin is flooded from the run-off from six main wadis (Sahawneh, 1996).

Three major tectonic phases, early Paleozoic, late Cretaceous and Eocene, caused the Al-Azraq Basin to be epeirogenic with subsidence in the Qa area

(Ibrahim, 1996). Al-Azraq-Sirhan graben was formed by the Al-Azraq Basin and separated from the basin by structural arch (Bender, 1975). The upper part of Balqa group is the bedrock formation of Al-Azraq basin.

Geological Setting of Al-Azraq Basin

The Al-Azraq Basin consists of Cretaceous and Tertiary limestone culminating in the Umm Rijam Formation, which contains nodular and tabular chert concretions (Bender, 1974; Sahawneh, 1996). These rocks are overlain by Oligocene and Pleistocene age basalts to the north and northeast of the basin (Ibrahim, 1996).

The presence of several faults surrounding the Qa area indicates the Qa depression is tectonic in origin (Ibrahim, 1996). Additionally, the Al-Azraq Basin is the northwest extension of the NW/SE strike slip fault of the Sirhan-Fuluq-Siwaqa fault system. The Siwaqa fault is an E/W striking fault stretching across the Jordan

Plateau from the Dead Sea to Saudi Arabia. The Siwaqa fault defines the southern

36 limit of the Al-Azraq Basin and separates the Al-Azraq Basin for the larger, longitudinal Wadi As Sirhan fault (Powell, 1989).

Hydrology of Al-Azraq Basin

The Al-Azraq Basin is the second largest basin in Jordan characterizes as endorheic (Davies, 2005b). Closed basins are very sensitive to changes in the watershed, particularly in arid settings (Renaut and Last, 1994). Bender (1975) identified a paleolake covering the area of the Al-Azraq Basin during the

Pleistocene. The sources of water recharge depend upon the depositions in paleolake as well as the watershed (Gustavson et al., 1995; Wood, 2000). In the area of Al-

Azraq Basin, basalt affects the chemistry of groundwater flow into Al-Azraq basin

(Davies, 2005a).

Flooding occurs in the Qa area of the Al-Azraq Basin during winter time that brings fresh to brackish water to the basin (Figure 3.5). This makes the basin a very vital stopover for the migratory wildfowl in Jordan (Bird Census Report, RSCN,

2003). The Al-Azraq basin offers very good quality of ground and surface water in

Jordan. The importance of the Al-Azraq Basin is as a major source of water for the cities of Amman and Zarqa which support three quarters of the population of Jordan.

The Al-Azraq Basin contains three aquifers: 1) an upper shallow freshwater aquifer contained in the basalt; 2) the middle is a brackish water limestone constrained aquifer; and 3) a deep sandstone aquifer (Agrar and Hydrotechnick,

1977). The Al-Azraq also has several springs, two in the Azraq Oasis located on the western margin of the Qa. The velocity of the groundwater flow from the recharge

37 area to the spring in the Azraq Oasis is very low (Naqa, 2010). Recent studies indicate the age of groundwater 30 km north of the oasis is 4,000 to 20,000 years old

(Naqa, 2010). Factors impact drainage networks such as soil type, structure and type of rocks. Ten wadis drain into the Al-Azraq depression and Wadi Rajil is the largest

(Naqa, 2010). The flow of groundwater is from north to south, and surface water from all directions drain into the Al-Azraq depression (NJWRIP, 1989).

Figure 3.5 Distribution of the drainages into the Al-Azraq basin. Modified from Naqa (2010).

Figure 3.6. Al-Azraq Basin in flood stage during winter time in 2010. The picture in the top (a.) is the flooded during winter time October 2010. Adapted from Naqa (2010). The bottom pictures (b. and c.) show the flooded Qa in October 1998.

Al-Azraq Climate

The climate in the Al-Azraq Basin has changed considerably over time. The modern climate has two seasons: 1) hot and dry summers, and 2) wet and cold 39 winters. The region of the study area is arid to semi-arid. Humidity in the Al-Azraq

Basin varies from summer to winter ranging between 49.9% - 61% and 56% -82%, respectively (Ayed, 1996). The average annual maximum temperature is 26.6 °C and the minimum is 11.6 °C. July 1979 recorded the highest temperature. However, the coldest (–9 °C) temperature occurred in January 1993 (Naqa, 2010). Most precipitation happens between January and March. The average precipitation in

Azraq Oasis and Jabal Arab is 50 mm/a and 500 mm/a, respectively. The sunshine in the Al-Azraq Basin in winter and summer is 8 -8.3 hrs/d and 8.7 -11.9 hrs/d, respectively. The daily evaporation ranges from 3-12 mm in winter to 5-19 mm in summer.

Paleoenvironment and Paleoclimate of the Al-Azraq Basin.

The presence of lake sediments in what is currently a semi-arid to arid region demonstrates the change in long-term climate and a record of lake history (Bender,

1974; Davies, 2000). During the Early and Mid-Holocene, arid lake sediments reflect changes in climate in Arabia peninsula (Davies, 2006; Parker et al., 2006). In addition, eolian deposits provide proxy records of changes in Quaternary climate

(Turner and Makhlouf, 2005; Davies personal observation).

Paleolakes on the Jordan Plateau provide long paleoenvironment records of climate change in the desert interior (Davies, 2000, and 2005a). Both the Al-Azraq and Al-Jafr basins are considered good areas for preserving the history of past environment and climate (Bender, 1974; Ibrahim, 1996). These sediments reflect changes in moisture, however, they behave inversely with sedimentology and

40 geochemical data (Davies, 2000, 2005a). Some studies identify the Early Pleistocene as warmer and wetter than the present (Abed et al., 2008; Turner and Makhlouf,

2005). This interpretation fits with interpretations of climate fluctuations of the

North African Sahara (COHMAP Members, 1988; Yan and Petit-Maire, 1994;

Gasse, 2000; Larrasoana et al., 2003), Arabia (McClure, 1976; Al-Sayari and Zötl,

1978; Fleitmann et al., 2003) and SE Asia (Zhuo et al., 1998).

Diatoms are algae that play an important role in understanding the past environment (Gasse, 2000). Diatoms are very sensitive to variation in ecological conditions and indicate changes in paleoenvironment and paleoclimate. Several primary and secondary factors affect these species such as: precipitation, solar output, wind strength, upwelling and erosion. In addition, diatoms can be good indicators for lake level and nutrient distribution. Benthic diatoms are abundant in nearshore waters; at shallow depths where light is available (Stone, 2004). However, planktonic diatoms are present below the open water (Wolin and Duthie, 1999).

Diatom species identified in the Al-Azraq Basin include Aulacoseira sp. and

Stephanodiscus sp. (Ahmad, 2010). In addition, Al Ali (1993) discovered some species of diatoms used for industrial purposes and some in clay deposits such as bentonite.

Archaeology and Geoarcheology of the Al-Azraq Basin

The archeology of Jordan has a long and rich history. It is very important in providing climate change information about throughout the Quaternary Period. The Quaternary is a very important period for archeology because it is during this time that modern humans

41 developed and civilization emerges (Cordova, 2007). According to Cordova (2007) and

Davies (2007) Transjordan had in the past a more moderate climate, abundant water, and fertile soil. Twentieth century scholars focused on changes in the ancient environment inhabited by early humans by using different proxies such as physical, chemical, and biological indicators. This section reviews the geoarchaeology of Jordan and how researchers use proxies to identify ancient human environments. The Al-Azraq basin played an important role in the human history of the region. Its springs were a source of water dating back to the

Acheulian period 200,000 to 400,000 yrs BP (Rollefson et al., 1997; Edgell, 2006).

The geoarchaeological approach to determining paleoenvironment includes analyzing sediment deposits inside and outside of archeological sites for fauna, vegetation, geomorphological processes, and the impact of humans on the environment (Cordova, 2007).

Different proxies contributing to the understanding of paleoenvironments include the shape, size, and arrangement of sediment of past fluvial environments (Cordova, 2007). There are many more climate indicators employed in the broad field of geoarchaeology such as pollen, diatoms, and geochemistry.

The Al-Azraq and Qa' Al-Jafr basin sediments reflect past lacustrine environments and periods of higher moisture that potentially played important roles in the human history of the eastern desert region of the Jordan Plateau (Ames and Cordova, 2012). Additionally, the lake phases of the basins may relate to critical periods in the history of human migration out of Africa and settlement in the Levant (Davies, 2005a; Petraglia et al., 2011; Ames and

Cordova, 2012). The Al-Azraq basin played an important role in the immigration of humans and animals since the (Grarard, 1998; Rollefson, 2000). The wetlands provided by the Al-

Azraq springs were a focus of human occupation, as well as a repository for environmental

42 information (Jones and Richter, 2011). The interbedded archaeological material provides additional age correlation for the associated paleoenvironments (Cordova et al., 2012).

While the wetland margins of the Al-Azraq extend into the Last Glacial Maximum (LGM) in the Druze marsh on the northern shore (Ames and Cordova, 2012; Cordova et al., 2012), the base of the basin may well represent much older climate transitions represented by the high moisture period of the earliest occupation of the Lion Spring of Late Acheulian age

(Rollenfson, 2000); or might it might reflect the paleoenvironment of Early to Middle

Pleistocene (Davies, 2005b).

Acheulian and Early Mousterian lithic artifacts found in Hammah and Al-Azraq

Oasis sediments represent Mid-Pleistocene and Late Pleistocene ages, respectively. In addition, these types of lithics are found in the vicinity of Qa' Al-Jafr and Ma'an, and also in some sites surrounding the Al-Azraq basin demonstrating the of significant age of exposures across this landscape (Davies, 2005b). It is very important to the archeological community to note that extensive Holocene sediment is no longer present in the Al-Azraq and Qa' al-Jafr basins (Davies, 2005b). However, the reason for the lack of Holocene sediment in the area remains unknown. It could be changes in depositional patterns or erosion activities that removed the Holocene sediments (Davies, 2005b).

Chronology of the Al-Azraq Basin

A small charcoal sample from AZ1, just below five meters, returned a radiocarbon age of 11,460 ± 40 B.P. (Davies, 2000). An additional radiocarbon age of Al-Azraq sediments comes from a 72 m sediment core of unknown location within the central qa area of the Al-Azraq basin (Cane, 1992). That dated sample,

43 also from the upper sediment (6.30 m), returned a similarly old near surface age of

~40,000 yr. From these ages is it interpreted that sediments of Holocene age are not broadly preserved across the central basin (Davies, 2005b).

Infrared Stimulated Luminescence (IRSL) analysis of sealed sediment samples at

0.20-0.28 m and 5.37-5.46 m produced ages of 24.2 ± 2.0 ka and 163.3 ± 11.7 ka, respectively (Davies, 2005b). IRSL ages for a sample at 11.62 m returned an age of greater than 250 ka (Davies, 2005b). This sample age is near the saturation point of the method, and should be considered a minimum age. The maximum age of the Al-Azraq basin sediments is unknown at the present and the basal sediments have not yet been recovered in cored sediments. However, based on the above ages from cored sediments, a chronology of Al-

Azraq lake basin is calibrated in Figure 3.7. The maximum ages of nearly 600 ka are extrapolated and should be consided preliminary.

Figure 3.7. The chronology of the Al-Azraq sediments. The gray line is based on a single radiocarbon date of calcite at 6.30 m below the surface (Cane, 1992); the black dashed line is based on three IRSL ages at 0.28 m, 5.46 m, and 11.66 m (Davies, 2005b).

Other age determinations from along the Al-Azraq margins including radiocarbon, optically stimulated luminescence (OSL), and Uranium-series ages from Azraq as-Shihan marsh along the western qa margin and 11 sections from the

Druze Marsh, a small basalt embayment along the northern boundary of the qa. The reported ages place these sediments at the Pleistocene-Holocene transition (Cordova,

2008, Cordova et al., 2013).

These sediments include the 'Ayn Qasiyya section ranging in age, based on radiocarbon ages, from 23,980 ka (calyr BP) to 9,610 ka (calyr BP), and based on

OSL ages from 62 ka to 2.7 ka (Jones and Richter, 2011; Tables 1 and 4, respectively). A summary of 'Ayn Qasiyya Uranium-Thorium (U-Th) series includes ages ranging between 118 and 93 ka (Cordova et al., 2009). The ’Ayn Sawda sediments record 16,132 and 15,372 BP radiocarbon ages, and OSL ages from 93 ka,

29 ka, and 1490 yr before 2007 (Cordova, 2008, Cordova et al., 2013). The Druze

Marsh located in the North West corner of Al-Azraq basin represents ages between

>38 ka and >29 ka from OSL age of two eolian samples (Cordova et al., 2012).

Druze Marsh deposits from U-series range in age of 151 to 12 ka on pedogenic carbonate (Cordova et al., 2012).

Additional ages for higher than present moisture outside the Al-Azraq central basin include Qa el-Mudawwara, approximately 176 km south of Al-Azraq near the

Saudi Arabian border, with U-Th ages between 170 and 152 ka, and equated to MIS

6 (Abed et al., 2000; Petit-Maire et al., 2002, 2010). Abed et al. (2008) also dated two samples of cardium from horizons at the top of the Al-Azraq formation in the eastern plateau near Umari, approximately 43 km south of Al-Azraq along the Saudi

Arabian border. This sample based on U-series returned an age of 330 ka which

Abed assigns to MIS 9. Turner and Makhlouf (2005) also provide ages for exposed lascutrine sediments from Umari dating approximately 600 ka.

CHAPTER 4

INTERPRETATION OF LACUSTRINE SEDIMENT

AND APPLIED METHODS

Introduction

This chapter will address methods used in this project including chemical composition, carbon and nitrogen cycles in lake sediments and other supported methods.

Understanding the processes of production and preservation of organic matter in sediments provides information about lake history. Also, this chapter will focus on arid lake sediments as area of the Al-Azraq basin is an arid paleolake. Additionally, the chapter will demonstrate the importance of methods used in this project interpretation of each method with procedures of samples preparing. Lake sediments potentially preserve a record of environments and anthropogenic environmental influence (Wolfe et al., 1999; Hammarland et al., 2005;

Mcfadden et al., 2005; Rasmussen and Anderson, 2005; and Talbot et al., 2006). However, alteration can affect the climate information and limit the available record. Stable isotope geochemistry indicates information about the past environment and the source of organic matter (Meyers, 2003, Cohen, 2003; and Last and Smol, 2001).

Arid Lake Sediments

Organic and inorganic sediment in arid lakes region provide faithful information about the paleoenvironment and paleoclimate. The transition zone of desert loess provides a good record of variation in climate during late Pleistocene in the North China (Sun et al.,

2013). Australian arid zone demonstrates changes in moisture across dry-land over the past

40,000 years (Fitzsimmons et al., 2012).

Organic Matter Content of Lacustrine Sediments (OC %)

Organic matter (OM) is preserved in sediments for millions of years reflecting conditions when the organisms lived. Even though lake sediments contain a low concentration of organic matter, it is sufficient to record the lake history. Organic matter in lake sediments is divided into two groups: vascular such as grass, shrubs, and trees plants and non-vascular such as phytoplankton (Meyers and Teranes, 2001). Organic carbon (OC) and total organic nitrogen (TON) together play an important role in distinguishing source of organic matter (OM) within the allochthonous or autochthonous. Autochthonous originates from the lake itself such as algae and plants, or precipitated biologically derived by CaCO3, whereas, allochthonous enters the lake from the catchment area in different forms such as dissolved, colloidal, and suspended forms (O’Sullivan, 2004). Therefore, OC identifies the primary production of OM and its degradation combined with allochthonous OM (Meyers and Teranes, 2001; Roth et al., 2004). Allochthonous OM appears in two forms: dissolved organic matter, and particular organic matter. In sediments, the form of OM is particular OM, however, in large carbon pool, the form of OM is dissolved OM (Dean, 1999). Cohen (2003) suggested that allochthonous sources might be abundant in shallow water, whereas, this proportion decreases because of the dissolution of the epilimnion. Therefore, this project analyzed % OC and % TON of the Al-Azraq core AZ1 to identify the distributions of organic matter throughout the paleolake sediments.

Sample Preparation

Measuring either total organic carbon (TOC %) or organic carbon content (OC %) determines the distribution of OM. The TOC is calculated by subtracting total inorganic carbon (TIC %) from total carbon (TC %). Calculations these two percentages is by

Coulometer. Calculating OC is measured by the Elemental Analysis (OC %) of analyzing bulk organic matter after removing carbonate from sediments (Meyers and Teranes, 2001).

Elemental Analysis used the instrument at the University of Kansas. The results revealed the distribution of OC % in the Al-Azraq sediments core AZ1, and total organic nitrogen (TON

%).

Carbon Isotopic Composition of lacustrine Organic Matter (δ13Corg‰)

Carbon isotopic composition is a vital proxy to assess paleoproductivity and determine the nutrients in the surface water (Dean, 1999; Filippi and Talbot, 2005;

Hammarlund et al., 2005, and Talbot et al., 2006).

Organic matter (20‰) produced by aquatic algae C3 is lighter than the carbon ratio of its DIC source; algae removes 12C from the lake, then the surface aquifer will be enriched in

13C (Craig, 1954; O’Leary, 1988; Lamb et al., 2006). Increase the uptake of photosynthesis of DIC leads to increase the heavy isotopic composition of organic matter. Therefore, increase production of lake organic matter makes the values of δ13Corg more depleted (Wolfe et al., 1999; Muzuka et al.; 2004; and Talbot et al., 2006). δ13Corg values reflect increase or decrease in productivity of the lake. The limit of lake organic matter affects the carbon isotopic composition of organic matter by making it mirror the isotopic composition of inflowing DIC; moreover, changes in temperature, pH, nutrients limitation, and growth rate

49 impact the carbon isotopic composition of organic matter (Meyers, 2003). Also, it is notable that C3 vascular and non-vascular plants are indistinguishable isotopically when the CO2 is the primary source of carbon (Meyers and Teranses, 2001).

Plants use three main pathways for photosynthesis: C3, C4, and CAM (O'Leary et al.,

1992). It is called C3 because the CO2 is first incorporated into a 3-carbon compound. The

C3 pathway uses the enzyme RuBP carboxylase (Rubisco) to reduce CO2 (Boutton, 1991).

12 13 Rubisco incorporates preferentially CO2 over CO2, thus C3 plants have low (more negative) δ13C values in the ratio of 13C/12C (-20‰ to -32‰) with an average of -27‰

(Boutton, 1991). However, C4 plants use the enzyme PEP carboxylase to reduce CO2. C4 plants have less negative δ13C, even though PEP carboxylase discriminates against 13C. The values of δ13C for the C4 pathway range between (-9‰ to -17‰), with an average of -13‰

(Boutton, 1991). It is called C4 because the CO2 is incorporated into a 4-carbon compound.

C3 is favored in high latitudes, cool and moist climates, and with more arid summers.

However, C4 plants are abundant in regions with summer rainfall (Sharp, 2007). C4 plants need high temperatures because CO2 is delivered directly to the Rubisco, not allowing it to grab oxygen and undergo photorespiration.

Finally, Crassulacean Acid Metabolism (CAM) is the third photosynthetic pathway.

The CO2 in this kind of plant is preserved as an acid (crassulacean acid) before being utilized in photosynthesis. The CO2 is converted to acid and stored at night while the stomata are open. During the day time the stomata are closed preventing water loss, the acid is broken down, and the CO2is released to Rubisco for photosynthesis.

The C3 and C4 respond to p(CO2) differently. C4 does well under low pCO2, and has high water competence, thus it resists high temperature and aridity (Sharp, 2007). However,

C3 requires high concentrations of pCO2. The situation of CAM plants is similar to C4 plants. They respond to high temperatures allowing this kind of plant to inhabit in arid conditions. CAM plants have δ13C values between those of C3 and C4 (Boutton, 1991).

Nitrogen Isotopic Composition of lacustrine Organic Matter (δ15Norg ‰)

+ - A source of nitrogen for primary production is ammonium (NH4 ), nitrate (NO3 ), and

- nitrite (NO2 ) which are important to dissolved inorganic nitrogen (DIN). Most phytoplankton utilizes dissolved nitrate, signaled by elevated δ15N values due to partial denitrification during water column stratification (Peters et al., 1978; Letolle, 1980; Muzuka, et al., 2004). However, land plants do not use atmospheric nitrogen (N2). It has to be converted into a form of NH+4, NO-3, or NO-2. Therefore, the values of nitrogen isotopic composition (δ15N) of land plants are low (Peters et al., 1978).

Nitrogen isotopic composition is an important proxy to determine source of organic matter in lake sediments (Herczeg et al., 2001; Talbot, 2001). It is also useful to identify the presence of nitrogen for aquatic primary production and production of organic matter

(Meyers and Teranes, 2001; Talbot, 2001; Watanabe et al., 2004; and McFedden et al.,

2005). Nitrate is the most common form of inorganic dissolved nitrogen that is used by algae; the signature of δ15N of nitrate is typically 7–10 ‰. However, plants utilize nitrogen fixation records δ15Norg with mean +5 ‰ (Meyers, 2003; Peterson and Howarth, 1987).

During a nitrogen limiting environment, 15N of the DIN pool will be enriched as a result of the uptake light nitrogen of organic matter. In this case, algae utilize DIN which leads to enrich the values of δ15N of nitrate and increases the values of δ15Norg of organic

15 matter (Routh et al., 2004). The removal of nitrate from the pool leads to increase δ NDIN

51 which makes the increase of δ15Norg (Meyers and Teranes, 2001). As a consequence, the

15 δ Norg values reflect the increase in organic productivity represented by high values, whereas low values indicate low productivity.

C/N Ratio of Lacustrine Sediments

Lake sediments contain different source of organic matter including aquatic, algae, and land plants which have diverse of nitrogen sources. Vascular and non-vascular plants record different C/N ratios such as 4-10 and greater than 20, respectively (Meyers, 1997;

Meyers and Lallier-Verges, 1999; Meyers and Teranes, 2001). Therefore, C/N ratio is a useful tool to identify the source of organic matter if it is from aquatic or terrestrial origin

(Meyers and Teranes, 2001; Lamb et al., 2006). The low C/N ratios can be reflected in the distance from the shore line (Meyers and Teranes, 2001). Thereby, low C/N ratios might be indicated at a location close to the shoreline, and as the distance from shore increases, the ratio also increases. High ratios of C/N indicate an increase of organic productivity, whereas variations in the ratios reflect low productivity (Routh et al., 2004).

Sample Isotope Preparation

Two hundred and twenty five samples were analyzed for Corg, carbon isotope composition, Ntotal, nitrogen isotope composition, and C/N ratio. The following procedure removed carbonate from the samples to prepare them for these analyses. The samples were prepared by the same procedure because all analyses required the same procedure. The procedure was adapted from the Paleoenvironmetal and Environmental Stable Isotope

Laboratory in the Department of Geology at the University of Kansas, The procedure for removing the carbonate from sediments is as the following:

Stable Isotope Sample Procedure

1. Drill Sample.

a. If the sample is pure carbonate, collect about 1 gram of the sample.

b. If the sample is non-pure carbonate/ paleosol, the amount collected should be

less than or equal to 1 gram.

c. If the sample is organic rich, such as black shale, weight 100-200 milligrams.

2. Weigh centrifuge tube without lid; record weights.

3. Weigh centrifuge tube without lid, plus sample; note weights.

4. Dry samples overnight and weigh, if there was a significant weight change or if you

know the samples are hydrophilic then dry for 48 hours.

5. Make 0.5M HCl (50 ml HCl from bottle added to 950mL millipure water.)

6. Add 30mL of 0.5M HCl, using the micropipette, to powder in a centrifuge tube.

Do this SLOWLY (carbonates will bubble up during this process).

7. With lid placed on top, but not screwed down, let sit for 30 minutes to an hour.

8. Repeat steps 1 through 7 for each sample.

9. Screw lids of the sample tubes on tight; shake each sample vigorously for about 5 to

15 seconds.

10. Over the course of the next 24 hours, repeat the following procedure approximately

every 4 hours:

a. Vent sample.

b. Rescuer sample.

c. Shake vigorously for 5-10 seconds.

11. At the end of the 24-hour period, shake all of the samples.

a. Samples that “fizz” are put into the “Acid” tray (still reacting).

b. Samples that do not “fizz” are put into the “Rinse 0” tray.

12. Place para-film over each of the samples before centrifuging.

13. Starting with the “Acid” tray, centrifuge four samples at a time at 4000 rpm for 5-10

minutes (or until sample is completely settled at bottom of tube).

14. Aspirate all the liquid from these samples and add 30mL of 0.5M HCl to each sample

tube.

15. Shake vigorously for 5 to 15 seconds.

a. If the sample does not “fizz”, the sample goes to “Rinse 0” tray.

b. If the sample does “fizz”, the sample goes to “Acid” tray.

16. For “Rinse 0” tray, centrifuge four samples at a time at 4000 rpm. Do this for 5 to 10

minutes, or until sample completely settles to the bottom of the tube.

17. After centrifuging is completed, aspirate off liquid from sample. Add 30mL of D.I.

water to sample tube.

18. Shake vigorously; making sure all sediment becomes suspended in D.I solution.

(Sometimes the sample will stick to the bottom of the tube.)

NOTE: If Samples are hydrophilic you may have to repeat rinse process twice (i.e. 6

rinses)

19. These tubes go to “Rinse 1” tray.

20. Repeat procedure in Steps 16-18 for “Rinse 1” samples. These samples will then be

placed in “Rinse 2” tray.

NOTE: Remember to place parafilm over each of the samples before each centrifuge

run.

21. The tubes in “Rinse 2” tray should then be centrifuged.

22. After centrifuging, check the pH of each sample.

a. If the sample solution is too acidic, check the pH of all the samples in the tray.

Place the acidic samples back into “Rinse 1” tray. They will need to be rinsed again

using the steps 16-18 listed above.

b. If samples have normal pH (6-7), aspirate water out. Place into “Oven” tray.

23. The “Oven” tray samples are placed into the “Isotemp Oven” until dry (determined

by non-variant weight). This typically takes 24 to 48 hours. Put the entire tray (which

is specially designed for the Isotemp Oven and holds 24 tubes) in the oven at 45

degrees Celsius. The lids should be thrown away before the sample tubes are placed

in the oven.

24. When dry, weigh sample plus tube and note.

25. Scrape the sample from the mold, and if necessary re-grind with pestle and mortar.

Store the samples separately in small, lidded glass vials with a volume of about 2mL).

After removing carbonate from the sediments, samples were weighed to 0.05

microgram and put it in a tin. Then the tin was sealed completely to prevent the

sample from getting out of the tin and to prevent contamination with other samples.

Now the sample is ready to analyze by Elemental Analysis (EA). These analyses were

completed in the Mass Spectrometry Laboratory at the University of Kansas.

13 18 Isotopic Composition of Calcium Carbonate (δ Ccarb‰ and δ Ocarb‰)

Oxygen and carbon isotopic composition of calcium carbonate is a useful tool to indicate changes in lake productivity and climate. Carbon and isotopic composition of carbonates from the catchment and suspended-load river input of Lake Kinneret (Israel) indicate the presence of allochthonous and autochthonous carbonate samples (Stiller, 1977)

Oxygen and Carbone isotopic composition of lacustrine carbonate are useful tools to predict the paleoclimatology and important to understand the lacustrine systems (Leng, 2006).

13 18 δ Ccarb and δ Ocarb reflect the source of carbonate and the paleo-water temperature, respectively. Both these isotopes are controlled by the hydrology of lake and water vapor exchange with the atmosphere (Talbot, 1990; Li and Ku, 1997; Dean, 1999; Mayer and

Schwark, 1999; Schwalb and Dean, 2002; Kirby et al., 2004; Hammarlund et al., 2005).

13 δ Ccarb values reflect the mixture of isotopic composition of DIC and fraction of

13 primary production within a lake. Moreover, δ Ccarb values indicate hydrological balance

13 and evaporation effects. δ Ccarb values of inflow DIC indicate its terrestrial origin with

13 depleted values; however, δ Ccarb values approximately +1 to 2‰ in rare case of isotopic equilibrium with atmospheric CO2 at 7‰ (Clark and Fritz, 1997). Carbon dioxide, formed by decomposition of soil organic matter, produces acidic soil when it is dissolved by rainfall.

δ13C, approximately -5, is from the dissolution of the total calcium carbonate by carbonic

13 acid. δ Ccarb values of biogenic calcium carbonate will be enriched as a result of removing the light carbon dioxide by autochthonous primary biogenic production. Isotopic composition of DIC change seasonally; the change is as a result of extraction 12C either in spring by the high photosynthesis or in warm summer by the evasion of CO2 gas (Ito, 2001). Also, mixing

56 low δ13C DIC (annual turnovers), which is from oxidized or respired organic matter in the bottom of the lake, change seasonally δ13C of DIC (Last and Smol, 2001).

The sum of water inflow minus the sum of water outflow indicates the hydrological lake balance by tracing of the isotopic composition of lake water. Evaporation enrichment and isotopic composition of input waters impact the oxygen isotope of lake water (Anderson et al 2001; Schwalb, 2002; Seppa et a.l.2005). Temperature and isotopic composition of lake water affect the oxygen isotopic composition values of authigenic precipitated carbonate

18 18 (δ Ocarb) (Eicher and Siegenthaler, 1976; Seppa et al., 2005). As a result, the δ Ocarb values are combined the oxygen isotope composition of lake water and the temperature during the

13 18 precipitation. δ Ccarb and δ Ocarb may reveal high values of allochthonous carbonate

(Hammarlund and Buchardt, 1996).

13 18 The covariance of δ Ccarb and δ Ocarb values are very useful to identify the hydrological open and closed systems (Talbot, 1990; Li & Ku, 1997). Closed system reveals

13 18 a strong covariance between δ Ccarb and δ Ocarb. There are two factors which affect this result: first is the impact of hydrological balance, and second is vapor exchange with atmospheric moisture. Both keep the water for a long time in a hydrological closed system.

13 18 δ Ccarb and δ Ocarb values indicate a rise in lake level in the hydrological closed system if

13 18 there is a difference in the δ Ccarb and δ Ocarb between the lake water and the inflowing water.

18 The δ Ocarb values of lake water give a signature for wet climate which is similar to

18 the δ Ocarb of the precipitation, if the inflow is high and evaporation is low (Mayer and

18 Schwark, 1999). The δ Ocarb will increase when the evaporation increases due to the light

16 13 O escaping. However, the δ Ccarb values increase when the evaporation increases and

57 inflow water reduces. The increase is due to the elimination of light carbon by photosynthesis and because of losing CO2 as a result of increase the evaporation which leads to increase the

13 18 partial pressure of carbon dioxide. As a consequence, increase of δ Ccarb and δ Ocarb values reflect the decrease in lake level (Li & Ku, 1997; Mayer and Schwark, 1999; Dean and

Schwalb, 2000). This situation dominates in a dry climate.

Sample Preparation

The preparation of a sample for carbon and oxygen isotope compositions requires the following steps. First, if sample X is mixed with an inorganic and biogenic carbonate, they must be separated from each other (Last and Smol, 2001). Second, the sample is placed in the oven overnight to make sure it is dried. Third, the sample is ground to a powder and packed into a vial (personal communication University of Kansas, Department of Geology teechnician). This preparation applies to samples for both carbon and oxygen isotopic composition of CaCO3.

The procedure for running a sample instrumentation is different from lab to lab, and depends on what type of machine being used. The preparation for this method is described by

McCrea (1950). The analysis is accomplished by the liberating CO2 in a reaction with 104% phosphoric acid. The carbonate reacts as little as a few tens of micrograms at elevated temperature 70 °C for a short time. It should include enough standard in the run’s day to ensure reproducibility and to normalize all values with respect to Vienna Pee Dee Belemnite

(PDB).

Magnetic Susceptibility

Magnetic susceptibility is a useful tool to identify the concentration of ferromagnetic minerals such as magnetite (Sandgren et al., 1990). Minerals and other materials accumulate in lakes by washing runoff from the surrounding of lake. The minerals and other materials are a consequence of erosion from catchment of the lake (Sandgren et al., 1990; McFeddan et al., 2005). Magnetic susceptibility indicates the presence of new materials enter lake pool either by rainfall or deformation or variation in lake levels. Distance from the shoreline affects the results of magnetic susceptibility. If the distance close to the shoreline, the results of magnetic susceptibility increase, however, the results decrease as long as increase the distance from the shoreline (McFeddan et al., 2005). Magnetic susceptibility is an important technique to differentiate diverse parts of the basin (Sandgren et al., 1990). In addition, it is linked to particle size such as clay and silt (Thompson, 1979).

Sample Preparation

Three sections have been sent to Limnology Research Center at the University of

Minnesota for magnetic susceptibility. The sections were cleaned and lined up on the machine for analysis. The High Resolution MS sensor is mounted on our Geotek XYZ scanner. The sensor itself is made by Bartington Instruments. The Unit that used in this analysis is SI x 10^-5.

Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES)

Trace and major elements are important analysis to determine the distribution of elements, and in terns to understand the paleoenvironment of lake. Some minerals reflect wet

59 climate, whereas others indicate dry climate. Ratios of some elements such as Na/Ti, K/Ti,

Na/Al, and K/Al of lacustrine sediments are used to determine human activities (Palanques, et al., 1998; Monica and Carlos, 2002). Allogenic elements such as Al, Ti, K, and Fe are connected to the surface chemical composition of lake surrounding which in turns are related to the lacustrine sediments. Deposition rate and chemical composition abundance are related to each other and both controlled by climate change and human activities (Dong, 2009). The ratio of Ba/Sr reflects increase in rainfall around a lake. Therefore, trace and major elements provide useful information to changes in climate of Al-Azraq paleolake.

Sample Preparation

Two hundred and forty five samples were analyzed for trace and major elements. The samples were collected from the core based on changes in lithology and sediment color. Five grams were taken from the core for each sample. Then the samples were left in oven under

45 °C overnight to remove moisture from the samples. Next, the samples were grinned to make powder and finally the samples were sieved through 80 mesh. Last result was two portions: first in the 80 mesh and second in the pan. The portion in the pan was sent for trace and major elements to ALS Minerals Company using Inductively Coupled Plasma Atomic

Emission Spectroscopy (ICP-AES).

Grain Size Analysis

One of the physical properties of sediments and soil is grain size. It has been used by different geological disciplines such as sedimentologists, geochemists, hydrologists, and engineers. In sedimentology, grain size analysis is used to find the relationship between the

60 grain size and transportation and deposits; whereas, geochemists use it to examine the kinetic reaction of particles and contamination; however, hydrologists utilize the grain size analysis when they examine the subsurface fluid; nevertheless, engineers measure the grain size to inspect the steadiness of soil or sediments (Blatt et al., 1972; McCave and Syvitski, 1991).

Based on these reasons, we can define the grain size analysis as determination or frequency distribution, and calculation of the statistical description that leads to identify the characteristics of sediments or soil.

Grain size analysis determines the percentages of clay, silt, and sand. However, during the analysis some calculations examine of the sediment particles. Particle diameter is measured which is called Mode; it has advantages to examine the transportation of sediments when there is more than one source of sediments, but the disadvantage of it is the its lack of the usage and it is hard to examine. Another calculation is called Median which means the half of particles is coarser and the other half are finer by the weight. Mean is the graphic measure that examines the overall sizes. Standard deviation is the best calculation to determine the sorting values of sediments. The best values of sediment sorting are between

20 to 25 phi. Kurtosis is the probability distribution relative to benchmark normal distribution by describing the degree of peakedness or flatness. Kurtosis of natural sediments is between

0.88 and 1.4. Finally, skewness is the independent of the sorting of the samples that measures the tails of the curve.

There is a scale that has been used to classify sediment particles. Udden-Wentworth is the scale that devised in 1922 to describe the grain size of sediments. This scale describes three groups of sediment particles including gravel, sand, and mud (silt and clay). The boundary between gravel and sand is 2000 microns; whereas, the boundary between sand and

61 silt is 62.5 microns; and finally, the boundary of clay is 3.9 microns. Moreover, it describes the sediments in more detail as very fine, fine, medium, and coarse particles. In addition to the grading scale, there are Folk and Shepard classification system. Both are reliable in order to classify particles size of sediments. However, Folk’s classification system is based on two diagrams, and uses the term mud instead of utilizing silt and clay. This division provides less detail about clay and silt. Folk system focuses on a function of high velocity of a current at the time of deposition beside the maximum grain size of debris that is present (Poppe et al.,

2000). On the other hand, Shepard’s classification system provides more details about the sediment classification which concentrates on the ratio of clay, silt, and sand (Poppe et al.,

2000). Instead of using both these programs classifications manually, USGS created a program called SEDCLASS that is naming the grain size by entering the percentages of clay, silt and sand to get the nomenclature for sediment grain size either of Folk or Shepard sediment classification systems.

Sample preparation varies based on the purpose of a study. In my case, I am working on sediment samples from a paleolake. This kind of sediment needs to get some treatments before we run the grain size analysis due to the incorporation of some components within or absorbed on minerals that alter the sediment texture (Vassma, 2008). Another problem might come up with the aggregation of fine grains (silt, clay) that takes place in aquatic environment called flocs (Van Rijn, 1993; Roberts et al., 1998; Kim et al., 2005). The composition and structure of these sediments modify temporally (Vassma, 2008) because they are cohesive (Hayter and Pakala, 1989; Paterson, 1997). Organic matter affects the grain size analysis (Vassma, 2008). For example, they might adsorb on a single grain, or form complex that reacts with iron (oxides) on the surface of the grains. Authigenic minerals

62 impact the grain size analysis, especially carbonate and diatoms that their diameter ranged from 5-200 microns (Round et al., 1990). Pre-treatment of samples for the grain size analysis is based on the purpose of the study. If we focused on delivery of allochthonous siliclastic materials, we need to remove carbonates, organic matter, and diatoms. Here there are two problems: one is the coarse grains which are easy to deal with by using sieving method to identify the grain size (Last, 2001). Second, fine grains might expose to flocculation, with damage grains by the pre-treatment and impact the result of the grain size analysis.

Thermal combustion is used to remove the organic matter from a sample. The dried sample is put in a crucible inside a muffle furnace after its weight is recorded. Then we measure the organic matter after we have heated to 550 °C (Boyle, 2001; Heiri et al., 2001).

This method seems easy; however, it might impact the sample as grain aggregate formation might take place (Murray, 2002).To prevent any damage to the grains, Hydrogen peroxide

(H2O2) 30% is the best way to eliminate organic matter (Schumacher, 2002; Allen and

Thornley, 2004). Moreover, we keep adding H2O2 to the sample until the frothing ceased, and also heat the sample into 80 °C to make sure all the organic matter was removed. When the reaction is finished, we wash the sample with distilled water by centrifuge (3500 rpm) and then we decant the solution.

Carbonate is removed by a thermal combustion method (Murray, 2002). Elimination of carbonates has been done by heating the sample to 950 °C for 2.5 hours (Boyle, 2001;

Heiri et al., 2001). Another approach to remove carbonates is to use hydrochloric acid

(Battarbee, 1986; Battarbee et al., 2001; Schumacher, 2002). The percentage of HCl depends on how much CaCO3 is in samples. In my project, I added 30 ml of 10%HCl to samples to remove the carbonates. Adding HCl is not only to remove CaCO3, but also to dissolve Al,

Mg, and Fe. After I made sure that there was not any trace of CaCO3 (doesn’t fizzes), I rinsed the samples with distilled water three times by using the centrifuge (3500rpm). It is more important to note that removing CaCO3 before the organic matter is better because removing

Fe makes organic oxidation faster, due to Fe is considered as catalyst of decay (Mikutta et al., 2005).

If the sediments contain diatom valves, they need to be removed by adding alkali

(Conley, 1998; Lyle and Lyle, 2002) such as 10 ml of 10% potassium hydroxide (KOH). A sample is pretreated in a water bath at 80 °C for 30 minutes. Then, the sample is washed with distilled water until it reaches its natural environment. Finally, hexametaphosphate is added to avoid grain flocculation (Murray, 2002; Andreola et al., 2004).

Now the sample is ready to use for grain size analysis by utilizing Coulter laser

Particle Analyzer LS2000. It is able to measure particles from 0.3 to 200 microns. Multiple analyses (9) run for each sample to make sure that the readings are consistent. A statistical analysis is made by the Coulter laser Particle Analyzer in an excel sheet. Coulter laser

Particle Analyzer fixes spatial angel by scattering laser-light. This mechanism depends on the physical property and angle of particles. The old method to determine the grain size is by using the hydrometer. However, this method is time consuming and not as accurate as

Coulter laser Particle Analyzer LS2000.

Smear Slide Technique

Thin section analysis is standard for geologists where 30mm thickness of materials on a slide allows precise birefringence as a device for the identification of minerals. However, smear slides of lake sediments have a large range of mud sizes starting from two microns to

64 the size of sand, and as a consequence wide and unfamiliar spectrums of birefringence behavior are present. This is problematic, however, the thickness and reflective indices can be estimated and provide clues for mineral identification and other microscopic objects such as organic matter, diatoms, pollen, and microfossils. Smear slides are an important method to quickly identify minerals and other microscopic objects in core sediments as a first look at the sediments as a guide to detailed sampling. Smear slides were prepared based on stratigraphic changes within horizons of similar grain size and color in Azraq sediment core

1. Two hundred samples represent this core. Slide preparation follows a procedure adapted from the Limnological Research Center, Core Facility (LRC) at the University of Minnesota.

Sample Procedure

1. Label a glass slide with all information about a core, drive, section, date, and depth of

sediments in centimeters.

2. Clean the glass slide by wiping down to remove dust or any contamination.

3. Place a drop of distilled water or alcohol on the slide. If a sample has high organic

matter, it is better to use distilled water, whereas, if it is high evaporate sediment, it

should use alcohol.

4. Using toothpick, take a small amount of sediment and mix it with the water or

alcohol.

5. Place the glass slide on a hot plate for 2 to 3 minutes. It is very important to make

sure the slide dries, so the slide acquires isotropic status.

6. Keep a bottle of Norland optical adhesive upside down to let the bubbles go to the

bottom of the bottle. This prevents them from being released onto the slide.

7. Drop 2 to 3 drops of the Norland optical adhesive on the sediment. Then add a 1in x

1in cover glass. Be careful to not touch the drops to prevent contamination. Also, do

not move the glass cover in different directions.

8. Place the slide under ultraviolet light for 1-2 minutes. The light used in this research

is a black light.

X-ray Diffraction

X-ray diffraction is used in this project as a tool to identify minerals and confirm smear slide observations. The main objective of this method is first to determine the minerals in these sediments, and second to identify which kinds of clay minerals are representative of the sediments. The selection of samples from the core depended on changes in the sediment's color and any changes observed in the grain size.

Powder X-Ray Diffraction analysis used a Rigaku MiniFlex diffractometer with Ni- filtered Cu Ka radiation at 30kV, 15mA. The samples were scanned at x° 2 theta/minute from

5 to 65°. The diffract grams were processed using Jade 8 software (Materials Data, Inc.,

Livermore. CA) etc. The following procedure was used to prepare two hundred and fifty four samples for X-Ray Diffraction.

Sample Procedure

1. Dry a sample on a hot plate until it is completely dry.

2. Grind the sample by agate mortar and pestle until it becomes a powder.

3. Put the sample in the circle spot and make the surface of the sample very smooth.

4. Now the sample is ready for X-ray diffraction.

Summary

The data interpretation scheme summarized below in a diagram modified after

Hammarlund et al. (2005) provides relative expressions of variables and their relationship to climate and lake levels (Figure 4.1). Carbon and oxygen isotopic composition provide information about paleohydrology by reflecting water residence time and the impact of precipitation as well as evaporation (Talbot and Kelts, 1990). Additionally, both theses proxies provide information about lake level changes (Talbot, 1990).

Organic productivity and nutrient supply can be estimated for lakes by carbon and nitrogen isotopic composition (Wolfe et al., 1999; McFadden et al., 2005). Also, fluctuation in lake water inflow causes changes in the both nutrient supplies and organic productivity

(Meyers, 1997; Talbot et al., 2006).

Figure 4.1 Data interpretation scheme for climate, lake levels, carbon and oxygen isotopic composition of carbonate, carbon and nitrogen isotopic composition of organic matter, and mineralogy for Al-Azraq AZ1 sediments. Modified from Hammarlund et al. (2005).

CHAPTER 5

RESULTS

Introduction

Al-Azraq sediment core AZ1 was recovered in 1997. It was initially described and examined in one meter intervals by Davies (2000). In this fine resolution study, changes in lithology and sediment color were the basis for collecting 500 samples at nearly10 cm intervals. The objective of the drilling was the reconstruction of a record of paleoenvironments and paleoclimate change on the interior of the Jordan Plateau. Initial core description was completed in the field by Dr. Davies with additional description in the laboratory. Several analytical methods applied to this core in the present study include: stable isotopic composition of organic and inorganic carbon, nitrogen, C/N, CaCO3 %, magnetic susceptibility, grain size analysis, X-ray Diffraction (XRD), and Scanning Electron

Microscope (SEM) (Table 5.1). The results of these analyses are described in the following sections.

Core Sediment Description

Al-Azraq sediment core AZ1 extends from the surface to 51 meters. The lithology of sediment varies throughout the core based. The description will be discussed by drives, each drive represents 3 meters.

Drive 1 (DR1) extends from the surface to 3m with a full 3 meters of recovery.

Sediments were very wet and difficult to handle. The first 20 cm sediments are a fine grained light yellowish brown (10 YR 6/4) with white nodules on the cut surface of the core.

Table 5.1 Analytical methods and number of samples used in this fine resolution project.

Methods # of Samples Smear Slide 180 Grain Size Analysis 250 Oxygen and Carbon Isotopes of Carbonate 148 Carbone and Nitrogen Isotopes of OM 325 ICPMS Major and Trace elements 225 Magnetic susceptibility 4 Sections X-ray Diffraction 225 SEM 5

1,358 Total Number of Samples

Sediments at 23 cm and at 31 cm are pale brown (6/3 10YR) and light brown (6/3 75YR), respectively. Remaining sediments are similar to the above with fluctuations between fine and medium grains. Also, the white nodules are present through the rest of the drive

(Appendix A).

Drive 2 extends from 3 to 4.50 m. The first 15 cm consists of moist clay. The color of this section is yellowish brown (10YR 5/4). The color changed to brown (7.5 YR 5/4) with increase in white nodules on the cut surface of the core sediments. Also, it has brown sediments deposited in vertical veins (Figure 5.1). Meter 4.06 to 4.40 again contained white deposits, possibly carbonate minerals. The last 10 cm is brown fine grained sediments with a presence of carbonate minerals as determined by reaction with hydrochloric acid.

Figure 5.1 Photograph of Drive 2 section with white sediment matrix, and vertical brown veins between 3 and 4.5 meters.

Drive 3 extends from 4.5 to 6 m, with 1.32 meters of sediment recovered during the drilling. The sediments fluctuate between medium and coarse grains with a few lenses of fine grains. Sediments are pale yellow in color changing to light brown along with some oxidation in the middle of the drive.

Drive 4 extends from 6 to 9 m, however, recovery was only 89 cm of sediment. Light brown color characterizes this drive with the presence of some white nodules on the cut surface of the core becoming a 15 cm thick layer.

Drive 5 extends from 9 to 9.50 m, but with zero recovery. There is not exact explanation about the missing section. However, there are some thoughts potentially could explain the situation. First, the machine may have hit an aquifer layer that is liquefying. The second possibility is this section could be a naturally occurring void.

Drive 6 extends from 9.50 to 12 m, with recovery of 1.44 meters. The first meter of this section comprises muddy sediments with very viscous consistency. Additionally, this meter may be a transition section due to changes in the lithology. The rest of the section until

12.5 m, the lithology changes to a reddish color. From 11.12 to 11.50 m the white nodules appeared on the cut surface of the core. However, the last 20 cm the lithology changes to increased clay with rhythmite lens (Appendix A).

Drive 7 extends from 12 to 12.50 m. The section is very short full with some maybe carbonate deposits. Dark greenish gray characterizes most of the section, but it changed to reddish brown at 12.26 m. The last 10 cm appeared as a chunk of clay with some carbonate deposits (Appendix A).

Drive 8 is 2.50 meters long, extending from 12 to 15 m. However, sediment recovery was only 0.66 cm. Sediments vary within this section. At 12 m sediments appear as greenish yellow with carbonate laminations appearing between 13.75 and 14.3 m (Figure 5.2 and

Appendix 4). The last 6 cm are carbonate deposits and clay sediments (Appendix A).

Figure 5.2 High resolution photograph of carbonate varves from meters 13.75 to 14.30 in Al- Azraq Core AZ1. Picture taken at the Limnological Research Center (LRC), University of Minnesota, Minneapolis.

Drive 9 extended from 15 to 16 m. The first 35 cm is similar to the previous section with increased carbonate deposits. However, the lithology changes to reddish color for the rest of the meter. In addition, vertical green veins appear throughout this meter. The last 10 meters are fragmented sediments (Appendix A).

Drive 10 covered two meters extending from 16 to 18 m. Sediment recovery was only

65 cm. Sediments are predominantly clay and sediment compaction could be affecting the recovery rate. The color of most sediment in this section is reddish brown, and varies to light reddish brown. The distinction of this section is the appearance of bright yellow veins throughout the two meters (Appendix A).

Drive 11 represents three meters extending from 18 to 21 meters with a sediment recovery of 1.83 meters. Grayish green (10Y 5GY 5/2) describes the first 20 cm. However, the next 30 cm changed to light greenish olive (10Y 5GY 6/2) and the section ends with carbonate deposits. White carbonate appears between 19.72 and 19.78 m. Laminations of white carbonate occurred at 20 m. The sediments in this meter are fine grained laminated into rhythmites with organic matter (Appendix A).

Drive 12 extends from 21 to 23 m and recovered 1.11 meters of sediment. Rhythmites of light and dark deposits characterize the first 20 cm of this section (Figure 5.3). The next 30 cm contain white deposits with yellow oxidation spots. The last section is green clay sediments with a 2 cm band of organic matter at 21.23 m (Appendix A).

Figure 5.3 Photograph of variations in deposition at 21 m of Al-Azraq sediment core AZ1.

Drive 13 was from 23 to 24 m and recovered the 52 cm remains of Drive 12. The core top was white limestone with gray to dark spots on the cut surface of the section. The rest of meter is layers of white limestone with 10 cm of green deposits. Drive 14 represents 24 to 27 m and recovered 1.05 meters of sediment. The first centimeter is dark green, followed by 58 cm of white deposits. The next 36 cm changed the color back to dark green until the end of the section. The section end contained sediment fragments. Salt also appeared with sediments

74 of this section. Fine grained sediments characterized this section within either the white or dark green deposits (Appendix A).

Drive 15 represents 27 to 30 meters, but recovered only five cm of sediment and much water. This section of the core could potentially represent a channel or part of an aquifer.

Drive 16 extended from 30 to 31.5 m and yielded only 13 cm which is the length of the core catcher attached to the bottom of the pipeline for each drive.

Drive 17 extends from 31.50 to 33 m recovering 94 cm of sediments. The first 15 cm are light green deposits of medium to coarse sediments. The next 23 cm the greenish olive sediments dominate with the presence of oxidations and convex layers. Fine grains and yellow deposits with some bands of organic matter occurred throughout the end of this section (Appendix A).

The lithology in the next section changes completely in comparison to the previous meters. The sediments are soft and the core easy to split. The sediments vary between sand, silt and clay.

Drive 18 represents 33 to 36 m. The first 20 cm of the section is laminated with light and dark deposits. The dark deposits appear to be organic matter. Also, this section ends with some oxidation of sediments. The next 28 cm alternates between light and dark sediments with the presence of two bands of organic matter and oxidation at 33.44 and 33.46 m. In addition, this section has brown veins composed of fine grained brown sediments. Light and dark sediments with some thin laminations of organic matter dominate the next 53 cm. Also, the fine brown veins continue in this section. The next 34 cm of the section is dominated by a large vertical fracture infilled with fine brown sediments. Oxidation occurs in the next 83 cm

75 in the form of bands of organic matter with yellow deposits at the end of the section.

Alternating light and dark deposits characterize the next section of 40 cm. At the beginning of 35.11 m the deposition of sediment becomes strongly angled to 22° and banded with organic matter. The strong 22° angle of deposition continues through the next 36 cm with some yellow deposits and brown veins. The fine brown veins increase in the last 34 cm appearing with pale yellow deposits at the end of 35 m. These three meters may contain diatoms (Appendix A).

Drive 19 extends from 36 to 39 m and recovered 1.86 meters. In general, this part of the core is very soft with yellow dots on the cut surface and very abundant diatoms. In this section, the sediments are light green to green in color. Thin bands of organic matter appeared from 36.13 to 36.25 m. The organic matter bands continue from meters 36.26 to

36.48 with 2 cm of organic matter with oxidation. This long section is rhythmites of light and dark green sediment (Appendix 4). A white layer, 7 cm thick appears at 36.49 m. The descriptions continued to the rest of section until the end of 38 m with laminations of dark and light green and oxidation occurring in some centimeters (Appendix A).

Drive 20 extends from 39 to 42 m recovering only 55 cm. The section was very soft and easy to drill. Sediments color is a brown gray with bands of organic matter and oxidation.

Drive 21 extends from 42 to 45 m with 2.87 m of sediment recovered. This section of the core contains rhythmites of dark and light green deposits with the presence of abundant diatoms. The first 65 cm of the section additionally contains oxidation and some bands of organic matter. The next 50 cm the rhythmites of light and dark green deposits continue with the presence of organic matter and ending with oxidized sediments. The next 92 cm begins

76 with 5 cm white deposits which are diatoms, and then again the rhythmites of light and dark green deposits. This kind of deposit continued to the end of the section in addition to the appearance of white diatom deposits at the end of this section. Moreover, some yellow deposits occurred in some centimeters of the section. Overall, the great abundance of diatoms characterizes this section of the core (Appendix A).

Drive 22 extends from 45 to 48 m with a sediment recovery of 2.36 meters. This section of the core is similar to the previous with an increase the dark green rhythmites. In addition, oxidation of sediments increased in some centimeters. The sediments are light to dark green and texture is clay to silt size. Lithology changed in the last 10 cm of this section appearing as light brown as fragments. This section is also full of diatoms (Appendix A).

Drive 23 extends from 48 to 51 m with recovered of sediments 2.35 meters. The first

15 cm are very dark and composed of organic matter. The texture of the sediments in this section is fine grained with the presence of yellow deposits. These deposits have a strong sulfur smell. There is also a presence of secondary gypsum in this section. Lithology then changes completely, becoming light brown deposits with the presence of particulate organic matter (POM). As depth increases down the core, carbonate deposits occur again along with some fine sand lenses. Also, some large grains, brown in color, occurred (Appendix A).

Smear Slides

Examination of one hundred and eighty smear slide samples determined the presence of specific minerals and fossils in the Al-Azraq core AZ1 sediments. Minerals identified in the smear slides are: carbonate, quartz, microcline and some species of diatoms. The following section discusses the description of materials identified in the smear slides.

Meters 1, 2 and 3 revealed some grains of carbonate. Small grains of carbonate appeared at 1.06 m (Figure 5.4). In addition, plants remain and possibly secondary gypsum occur.

Figure 5.4 Photograph and microscope (polarizing) image of fine carbonate grains in 1.06 m in the Al-Azraq sediment core AZ1.

The next 1.5 meters contain fish scales and plant remains, but fewer carbonate grains

(Figure 5.5). Again, smear slides reveal the presence of authigenic carbonate (Figure 5.6a) with gypsum and hematite (Figure 5.6b and c) in addition to some quartz grains at 4.5 to 6 m.

Another form of carbonate appearing in this section of the core is ooid in which the nucleus appears in the middle of the grains (Figure 5.6d). Authigenic carbonate continues from 6 to 9 m along with some grains of quartz (5.6 b) and gypsum (5.6 e). Carbonate is less abundant

78 from 9 to 12 m with the presence of gypsum and some needles in the matrix of the slides.

Also, the smear slide revealed some fossils in the bottom of this meter (Figure 5.7).

Figure 5.5 Photograph of carbonate grains occurring at 3.59 m in Al-Azraq sediment core AZ1. Cross polarized transmitted light.

• • "I " • , " . • , '.~ . " • •• • • • •

Figure 5.6 Photographs of minerals identified in sediments of the Al-Azraq core AZ1 from 4.5 to 6 m: a-1. Hematite without polarizer, a-2. Hematite with polarizer, b. Quartz grain, c. Hematite, d. Ooid or nuclei of carbonate, and e. Gypsum.

A few grains of carbonate appear from 12 to 12.50 m. In addition, some grains of gypsum and hematite occur in the section. The most interesting observations in this section are again the presence of some fossils (Figure 5.7). At the base of the section, where laminations of carbonate occur Smear slides revealed grains of clear authigenic carbonate occurring in the laminated layers (Figure 5.8). Large carbonate grains with dark center nuclei occur between 13 to 16 m (Figure 5.9).

Figure 5.7 Photomicrographs of authigenic carbonate exposed to diagenesis and possible foraminifera fossils. Cross-polarized transmitted light

Figure 5.8. Photomicrographs with non-polarized (top) and polarized light (bottom) of clear grains of authigenic carbonate present at 14.80 m.

Revealed in smear slides from 31 to 48 m is the presence of two different species of diatoms with some clay and organic matter. The two types of diatoms are the centric

Stephanodiscus sp. and the elongate Aulacoseira sp. (Figure 5.10). Most the diatom frustules in this section are broken. Identified in smear slides are different types of minerals in the last three meters of the Al-Azraq core AZ1. The most important characterization of this section is the appearance of the mineral feldspar in the form of microcline grains (KAlSi3O8) (Figure

5.11). It is potassium-rich alkali feldspar containing small amounts of sodium.

Figure 5.9. Photographs of carbonate diagenesis grains at 23 m.

Figure 5.10. Photographs of centric and elongate diatoms identified as Stephnaodiscus sp. and Aulacoseira sp. at 35 m. Most of the diatoms are severely broken.

Figure 5.11. Polarized light photograph of grains of microcline and carbonate.

Grain Size Analysis

Grain size analysis is an important proxy used to determine the distribution of grain size and thereby depositional energy environments. Grain size analysis, conducted on two hundred and fifty sediments samples from core AZ1, determined the variation of size distribution throughout the core. Silt dominated the core sediments averaging 63.66% (Figure

5.12). The average percentages of clay and sand were nearly equal at 18.03% and 18.30%, respectively.

In the first two meters (0-2 m) of the core sediments the mean grain size decreases as a result of decreases in the silt and sand percentages, whereas clay percentages increase with an average 35.79 % (Figure 5.13).

Figure 5.12 Diagram of clay, silt, and sand percentages from the grain size analysis of Al- Azraq core AZ1.

The mean grain size increases from 2 to 9.50 m and peaks to 82.40 % at 8.83 m. This increase corresponds with increases in the percentages of silt and sand, and a concomitant decrease in clay percentage (Figure 5.13). At 9.87 m, the clay percentage peaks at 66.66 % with decreases in the silt and sand percentages to 14.97% and 18.36%, respectively. From 10 to 25 meters, clay percentages increase slightly with an average of 20.12 %, whereas silt and sand percentages increase lightly to 62.04% and 34.36%, respectively (Figure 5.13). Sand percentage peaks to 71.90% at 25.23 m with decreases in the percentages of clay and silt to

1.86% and 26.18%, respectively. Mean grain size then fluctuates after this depth until 42 m with oscillations in the percentages of clay, silt, and sand. The percentages of silt from 42 to

52 m remain in a tight oscillation similar to the previous section. However, the percentage of clay decreases and sand increases which lead to an increase in the overall mean grain size

(Figure 5.13 and Appendix B).

Figure 5.13. Distribution of clay, silt, sand, and mean grain size of Al-Azraq core AZ1.

Magnetic Susceptibility

Magnetic susceptibility is a useful tool in determining the magnetic inputs of material to a basin from the lake catchment (Table 5.2). Magnetic susceptibility analysis of four core sections revealed a variety of magnetic peaks in some centimeters. The first section section

86 analysized rhythmites of carbonate from 13 and 14 m (Figure 5.12 a). The data reveal the presence of ferromagnesium minerals with consistant values . There is a major shift to 10

(SI*10ˆ-5) at the end of the section. The second section represents the first 32 cm of 21 m.

The data show a peak the curve in the beginning and the end of the section; however, it increases to almost zero with the presence of carbonate. The avarage increase in the top and bottom of the section is 7 (SI*10ˆ-5) (Figure 5.12b).

Table 5.2. Important Ferromagnetic Minerals with Susceptibility Index.

The third section represents 20 cm of 45 m extending from 45.78 to 45.98 meters.

The first 10 cm present a low magnetic susceptibility averaging 2.5 (SI*10ˆ-5) where there is an abandance of diatoms (Figure 5.12c). However, the value doubles for 3 cm where dark green deposits occur (Figure 5.12c). Then the data again record low susceptibility to the end of this section. Finally, the last section represents the 47 m. It extends from 47.35 to 47.65 meters. Magnetic susceptibility registers low values for the first 20 cm. At 47.49 to 47.53 meters, the susceptibility increased slightly to 10 (SI*10ˆ-5), again with the appearance of the dark green sediments. Then the data peak to over 20 (SI*10ˆ-5) in the presence of dark green sediments with some oxidation. The magnetic susceptibility shifts back to 10 (SI*10ˆ-5) from

87 meters 47.57 to 47.63. Finally, the remains section records low magnetic susceptibility

(Figure 5.12 d).

~ IIIKeptlbllIty 151.10"-5) macM1lc suKeptlblltty (SI_ 10"-51 1 5 7 o 10

U.80

14.0 E E 21168 14.2 1 1 21.218 14.4

14.6 21.268

14.71 21.318 a. b.

macnetk SUKeptibiNty maan. t1c s u scept1blllty (Sill 10") (51 II 10A) 0510152025 O.S 2 .S 4 .S 6 .5 4 5 .76 45.78 45.8 45.82 _ 45.84 E 47.49 ! 45.86 1- 47.51 45 47.53 1 .88 45.9 47.55 47.57 45.92 47.59 45.94 47.61 47.63 45.96 C. 4 5 .98 d.

Figure 5.14 Magnetic susceptibility graphs of four sections in the Al-Azraq core AZ1. a. rhythmites of carbonate at the end of 13m and beginning of 14 m; b. 32 cm of the beginning of 21 m; c. and d. 45 m and 47 m, respectively

Organic Carbon Content (OC %)

Organic carbon percentage reveals the variation in distribution of organic matter in

Al-Azraq sediment core AZ1. Overall, the percentage of organic carbon reflects low concentrations throughout the entire core except in a few meters at the bottom of the core.

The percentage of OC increases steadily with depth from 37 through 45 meters with average values starting at 0.17% and reaching 0.40% (Figure 5.13 and Appendix D). At 45 m the

%OC doubles to 0.68%. With increasing depth the organic carbon concentrations continue to elevate averaging 0.59% from 46 to 47 m with two peaks reaching 1.17% and 1.08% at 47.80 m. At 48 m the organic carbon concentration peaks sharply to 4.36% from an average of

0.40%. This is the highest concentration of organic matter registered in the core sediments.

At meter 49 and 50, the concentrations of organic carbon decrease abruptly back to 0.41%, and 0.32%, respectively (Figure 5.13 and Appendix D).

Total Nitrogen Percentage of Organic Matter (%Ntotal)

Again concentration of total nitrogen of the organic matter is very low throughout the entire core except in samples from the lower core sediments. As a subset of organic carbon abundance, the %Ntotal results overall are auto-correlated with the %OC and their graphs are similar. Total nitrogen values range from 01% to 0.18% (Figure 5.13 and Appendix D).

The concentration of Ntotal varies between 0.04% and 0.05% from 31 to 33 meters. The values show a similar increase in percent with increasing depth to the %OC. The rest of the meter is constant at 0.05%. At 35 m concentrations range from 0.04% to 0.07%, whereas 36 and 37 meters range from 0.05% to 0.07%, respectively. Concentrations for 38, 39, 40, and

41 meters range from 0.05% to 0.07%. However, concentrations at 42 m fluctuate between

~ ,,~ • , • • • I • ,,- U ." .""""" .n ·11 ·tt .. ' .. ,.' .... • ..."' ")II,, ..

~ " ? • " ~

0 r " S-

O < C- O , " ," " " ~ " ~ " " ~ " ). " " .... ~ " I;' Ii' ~ " -~ , ~. , It

5.15 Diagram of the geochemical data of Al-Azraq Core 1, including: %OC, %N, 13Corg, 15N, C/N vs. Depth (m) 91

0.05 and 0.06%. Concentration values for 43 to 48 continue to increase ranging from 0.04% to 0.11%, respectively. At 48.90 m the concentration peaks to its highest value at 0.18%.

Finally, from 49 to 50 meters the concentrations are lower, ranging from 0.2% to 0.05%

(Figure 5.13 and Appendix D).

Carbon Isotopic Composition of Organic Matter (δ13Corg‰)

The carbon isotopic composition varies throughout sediment core AZ1. It ranges from a high of -17‰ to a low of -26‰ (Figure 5.13 and Appendix D). At 31 m, the values of carbon isotopic composition range from –21.71‰ to -22.69‰, whereas meter 32 shows more depletion in the values ranging from -23.60‰ to -20.64‰. Meter 33 reveals a slight difference from the previous meters. The values range from -23.44‰ to -18.63‰, however they increased at some depths such as -18.63‰, -19.60‰, -19.59‰, and -19.14‰ at meters

33.27, 33.44, 33.46, and 33.76, respectively

At 34 and 35 m, the values vary only slightly from -23.75‰ to -20.02‰. Carbon isotopic values for 36 m range even more tightly between -20.93 to -20.24‰. The carbon isotopic composition signature of 37 m records a slightly less negative range from -20.97‰ to -19.28. The signature for 38 to 40 m ranges from -22‰ to -20‰, whereas 41 to 41.5 meters reveal less negative values in some levels (Figure 5.13 and Appendix D).

As the depth increases, 41.88 to 48 meters register less negative values of carbon isotopic composition as the organic carbon concentrations increase in these meters. The carbon isotopic values record more negative values from 48 to 50 meters. The values range

-25.54‰ to -22.16‰ (Figure 5.13 and Appendix D).

Nitrogen Isotopic Composition (δ15Norg ‰)

Values of nitrogen isotopic composition (δ15N org) fluctuate throughout the Al-Azraq sediment core AZ1. High values of nitrogen isotopic composition (δ15N org) in meter 3 ranges from 5.92‰ to 8.08‰. However, meters 32, 33, and 34 record values lower than the previous meter with five values ranging from 5.08‰ to 5.72‰. δ15N org values increase at meter 35 ranging from 5.79‰ to 6.49‰, whereas the values of δ15N org decrease slightly at meter 36 (Figure 5.13 and Appendix D).

From 37 to 43 meters, nitrogen isotopic composition of sediment organic matter (δ15N org) record values ranging between 5‰ to 6‰. However, meters 43 to 46.62 record low values of δ15Norg with increasing organic carbon concentrations. The values range from

3.71‰ to 4.97‰, the following values fluctuate between 4, 5, and 6 until the end of meter

47. Meters 47.80 to 51 record high values of δ15Norg with an increase the organic concentrations (Figure 5-13 and Appendix D).

C/N Ratios of Organic Matter

C/N ratios of sediment organic matter reveal slightly low ratios throughout the Al-

Azraq core AZ1 compared to Al-Azraq core 3. Variation in the C/N ratio values identifies five groups of organic sediments fromAZ1 (Figure 5.13 and Appendix D). The first group comprising the majority of the core sediments extends from 31 to 42.13 meters. The ratios in these meters are low and consistently range between 2.28 to 4.46. The second group extends from 42.26 to 44.86 meters and has C/N ratios ranging from 5.60 to 9.40. These ratios increase concurrently with increases in organic carbon concentrations. The third group extends from 45.05 to 47.76 meters with ratios increasing slightly with ranges of 8.99 to

12.96, also accompanied by simultaneous increases in organic carbon concentrations.

Extending from 47.90 to 48.90 meters, the fourth group has the highest ration of C/N ratios ranging from 10 to 27.71. The highest peaks of 23.63 and 27.71 occur at 48.81 and 48.90 meters, respectively. The final group extends from 48.99 to 50.35 meters, returns to low C/N ratios ranging from 6.40 to 14.23 similar to the second group. However, some samples peak to 13.00, 14.23, 11.88, 12.11, and 12.35 at meters 49.16, 49.92, 49.97, 50.06, and 50.24, respectively (Figure 5.13 and Appendix D).

Calcium Carbonate Content in Sediments (CaCO3 %)

One hundred and forty-eight samples determined the varying concentrations of calcium carbonate from the Al-Azraq sediment core AZ1. From 1 to 5.74 meters, calcium carbonate concentrations fluctuate ranging from 34.09 % to 48.86%. From 6.06 to 8.46 meters, values range from 53.11% to a high of 86.30%. This is the highest concentration recorded in the core sediments. The concentrations of calcium carbonate fluctuate and decrease as the depth increases from 8.83 to 16.33 meters decreasing from 50.33% to

16.68%. (Figure 5.14 and Appendix E). Calcium carbonate increases slightly with some minor fluctuations from 16.98 to 19.77 meters with values ranging from 27.62% to 63.20%.

However, an abrupt decrease and increase appears at 20.26 and 20.60 meters dropping to

3.91% and dramatically increasing to 93.06%, respectively. Finally, 20.72 to 31.58 meters reveals concentrations of calcium carbonate ranging from 31.55% to a high of 83.06% at

24.82 m. Below 31.58 m no calcium carbonate is present in the core sediments (Figure 5.14 and Appendix E).

Figure 5.16. Diagrams presenting distributions of carbonate calcium (CaCO3) and the carbonate and oxygen isotopes of carbonate throughout the Al-Azraq sediment core AZ1.

13 18 Oxygen and Carbon Isotopic Compositions of Carbonate (δ Ccarb & δ Ocarb‰)

Values of carbon and oxygen isotopes from carbonate vary throughout the Al-Azraq core AZ1 recording low and high values of carbon and oxygen, respectively. From 1 to 3.16

18 meters the values of carbon and oxygen isotope record are both low; δ Ocarb ranges from

13 0.29‰ to 3.02‰, whereas δ Ccarb are from -5.15‰ to -2.64‰ (Figure 5.14 and Appendix

18 E). However, δ Ocarb values increase sharply from meters 3.37 to 11.65 ranging from 3.50‰

13 to 5.80‰, whereas δ Ccarb continues to registers negative values ranging from -6.27‰ to -

18 2.47‰. From 11.67 to 12.43 meters, δ Ocarb decreases with negative values ranging from

13 -1.48‰ to -4.86 ‰, whereas δ Ccarb values range from -.479‰ to -2.95‰. In meters 12.54

18 13 to 14.77 δ Ocarb values reveal almost constant values at -3.0‰, whereas δ Ccarb obtained high values ranging from 3.70‰ to 5.14‰ with a sharp decrease to 1.32‰ at 12.95 m. In addition, other abrupt decreases occur at 14.89 m at -1.75‰ (Figure 5.14 and Appendix E).

18 Meters 15 to 31 reveal almost constant values of δ Ocarb ranging from 2.53‰ to 4.28‰.

13 However, meters 15 to 17.94 record less negative values of δ Ccarb ranging from -2.56‰ to -

13 1.02‰. The δ Ccarb reveal more negative values from 18.16 to 31.58 meters ranging from -

4.75‰ to -2.48‰ (Figure 5.14 and Appendix E).

Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES)

The cored sediments from the Al-Azraq Basin show variations in major and trace elements. Thirty-four elements analyzed using ICP-AES include major elements: As, Ca, K,

Mg, Na, S, Fe, and Ti (%), and the following trace elements: As, B, Ba, Cd, Cu, Ni, P, Pb, Sr,

Mn, V, and Zn (ppm) (Figure 5.15 and Appendix F). Measured concentrations are by percentages (%) and ppm units. Also, determining the Chemical Index of Alteration (CIA) contributes to understanding weathering rates in the basin (Roy, 2010) (Figure 5.3).

Additionally, ratios calculated for some elements provide more robust relationships.

The geochemistry of the major and trace elements varies throughout the lacustrine sediments. High concentrations of Ca, Mg, K, and Al, and low concentrations of Na, Fe characterizes the upper part of core sediments extending from 1 to 31.69 meters (Figure

5.15).

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0 • ,.. z• -

0 • ,.. '"~ •

. ",--~------.

( w ) 4 1daQ

Figure 5.17. Geochemical major elements including Al%, a%, Mg%, Na%, Fe%, and S%

However, the opposite occurs with high concentrations of Na, Fe, and Al, and low concentration of C, Mg, K characterizing the lower part of AZ1, extending from 32 to 50 meters (Figure 5.15). In general, the CIA for these elements describes low values. However, the upper part of the core (0 to 31.5m) contained lower values with an average 17.71 than the lower part of the core (31.5 to 51) with an average 23.70. Moreover, the values range from

4% to 40% in the entire core (Appendix F). Sulfur concentrations (S%) are constant, low concentrations throughout the Al-Azraq core AZ1 ranging from 0.1% to 0.38%. However, some samples peak to 1.11 % and 2.37 % in meters 4.2 and 48.03, respectively (Figure 5.15 and Appendix F).

Trace elements also demonstrate variation throughout the core sediments. As has low concentrations in the core ranging from 2 ppm to 20 ppm. From 1 to 31 meters, as was very low, then increased from 32 to 47 meters. However, it decreases again from 48 to 51 meters.

B is high (over 30 ppm) in the upper part of the core, whereas it is equal to or lower than 20 in the lower part of the core. Ba is high compared to B. It records high concentrations from 1 to 31 meters ranging from 200 ppm to 800 ppm. However, the concentrations decrease from

32 to 47 meters, and again it increases to over 200 ppm (Figure 5.15 and Appendix F). Cd,

Co, Cr, and Cu record very low concentrations throughout the entire core sediments. The trace element with the highest concentration is P ranging from 830 ppm to 2500 pm, whereas

Ni, and Pb register concentrations lower than 60 ppm (Figure 5.3 and Appendix 4). In addition, Sr demonstrates high concentrations as well, ranging from 150 ppm to 752 ppm. V occurs in moderate concentrations ranging from 80 ppm to 471 ppm (Figure 5.15).

CHAPTER 6

STATISTICS ANALYSIS

RESULTS AND DISCUSSIONS

Introduction

The purpose of this chapter is to determine the reliability of the data through statistical analysis using MATLAB. Statistics are a separate approach for analyzing the relationships of the data, can define correlations and highlight outliers (Hill and Lewicki,

2006). The application of statistics provides a robust basis for grouping similar environmental zones and comparing these zones through time. Cluster Analysis grouped individual major and trace elements, elements by depth and grain size fractions. The program used for the statistical analysis is matrix lap (MATLAB).

Cluster Analysis

Cluster Analysis uses algorithms to partition a set of variables into groups (Tryon,

1939). The specific application was k-Means clustering that minimizes variability within the clusters and maximize variability between clusters. In order to determine the clusters in

MATLAB, three steps are followed: 1) identify the distance between objects using pdist function. This step calculates the distance between every pair of objects; 2) the pairs of objects which are closest to each other link together by using linkage function. This step creates the hierarchical cluster tree; 3) divides the objects in the hierarchical tree into cluster groups by utilizing the cluster function. The following sections will discuss the results of

Cluster Analysis.

Clusters of Major and Trace Elements

Al-Azraq AZ1 major element concentrations were determined for 255 samples ranging from 0 to 51 meters and including: Al, Ca, K, Mg, Na, S, Fe, and Ti. The results were applied to Cluster Analysis to identify similarities and differences between the major elements using percentage. Cluster Analysis of the trace elements includes: Co, B, Ba, Cr,

Cu, Ni, P, Sr, V, Zn, and Mn. The results of the major element clustering revealed two major groups. Ca and Mg dominate one cluster (Figure 6.1). These two elements are the basis for the carbonate landscape in which the Al-Azraq Basin is formed. The bedrock for much of the

Jordan Plateau is composed of thick limestones formed during transgressions and regressions of the Tethys Sea throughout the Cretaceous Period (Bender, 1975). Ca and Mg occur as carbonate minerals in high concentrations throughout the core sediments, and are representative of precipitation products during arid periods. The second cluster group contains two subgroups, comprised of S, Ti, K and Al, Fe, and Na representing weathering products. Grain size analysis, to be discussed more fully later, supports the weathering product interpretation of this grouping because the grain size increases concurrently with the increase in weathering elements

Cluster analysis grouped eleven trace elements by ppm: Cr, Ni, B, Co, Cu, V, Zn, Ba,

Sr, and P into a nested hierarchy of groups. The most tightly clustered group contains Cr, Ni,

B, Co, Cu, V, and Zn. The elements of this group are all metals occurring in very low concentrations throughout core sediments. The next higher groupings of trace elements are based on increasing levels of concentration and include Ba, Sr, and P, respectively (Figure

6.2).

100

Figure 6.1. Clustering of major elements of Al-Azraq AZ1 core sediment identifies two major clusters. The second cluster contains two subgroups of major elements.

Figure 6.2. Clustering of trace elements of Al-Azraq AZ1 core sediment identifying one major cluster based on very low concentration levels and successive nesting clusters of increasing concentrations.

101

Clustering of all elements by depth identifies depositional groups of similar elemental composition. These clustered groups can then be examined, potentially identified similar environments (Figure 6.3). Two hundred fifty-five samples were clustered into 30 points representing multiple depths of similar elemental composition (Appendix G). The clustering revealed two major groups. Group 1 represents high moisture environments and contains three subgroups. Subgroup 1A includes points 22, 23, 19, and 21, identifying continuous sedimentation from 31 to 39 meters and representing the paleolake environments (Appendix

G). Subgroup 1B includes points 24, 28, 26, and 27 and represents transitional moistures phases from depths throughout the core including some surface horizons. Points 26, 27, and

28 represent continuous deposition from 41 to 48 meters. These intervals represent increased moisture in the transition from marsh to lake environments. Point 24 represents this phase as well as some near surface horizons. An example of transitional moisture phases in the near surface sediments might be represented by the seasonal winter flooding as seen in Figure 3.6.

Subgroup 1C includes points 29 and 30 which correspond to 48 to 50 meters and represents marsh deposits (Appendix G). These meters are lithologically similar and represent the maximum extent of the lacustrine phase.

Group 2 represents alluvial inputs to the basin of terrestrial materials, arid eolian, and evaporative environments contained in four subgroups. The four subgroups cluster elements by depth decreasing from the surface to 31.5 meters. Subgroup 2A, points 1, 9, 20, 17, 25, and 4 represent the modern surface to 5 meters below the surface and is indicative of mixed alluvial and eolian inputs to the basin. Subgroup 2B, points 2, 7, 3, and 5 represent depths from 6 to 15 meters, and also represents mixed alluvial and eolian inputs.

102

Figure 6.3. Clustering by depth of major and trace elements of the Al-Azraq AZ1. Group 1 represents higher moisture environments with three subgroups (1A, 1B, and 1C) reflecting lake phase, transitional phases and marsh environments. Group 2 (2A, 2B, 2C, and 2D) represents alluvial and eolian inputs of terrestrial materials to the basin and evaporative arid phases.

Subgroup 2C, points 6, 8, 10, 11, 12, and 16 represent depths 16 to 28 meters and is indicative of evaporative horizons of carbonate, specifically dolomite.

This phase reflects the highest levels of evaporation and most arid environment with eolian inputs of terrestrial material. Subgroup 2D, points 13, 14, 15, and 18, overlap with 2C depth ranging from 23 to 28 meters. Subgroup 2D represents less severe evaporation and eolian environments.

Cluster Analysis of Stable Isotopes Geochemistry Data

Three hundred and twenty five samples of bulk organic matter clustered to identify

13 common groups of geochemical data. Five variables, including % OC, % Norg, δ Corg, and

103

15 δ Norg, and C/N ratio, were analyzed to determine their closest relationships (Figure 6.4).

The clustering reveals expected results in the combination of chemical elements. Percent Norg and %OC represent the first cluster. This clustering confirms the source of nitrogen is from organic nitrogen. Also, this result reveals the close correlation between %Norg and %OC.

15 Another cluster combines δ Norg and C/N supporting their close correlation (Figure 6.4).

These findings support the use of these variables in identifying sources of organic matter.

13 However, δ Corg values grouped by itself because the values for this variable are negative.

Figure 6.4. Clustering of stable isotope geochemistry of bulk organic matter of Al-Azraq AZ1. The clusters demonstrate close correlation between isotopic variables and support their use as proxies for determining sources of organic matter.

104

CHAPTER 7

DISCUSSION

Introduction

This chapter discusses interpretations of the multiple proxy data generated from the

Al-Azraq sediment core AZ1. These interpretations are placed in the context of paleoenvironment and paleoclimate implications for the Al-Azraq Basin and Jordan Plateau in general. During the Quaternary Epoch, Earth’s fluctuating global climate impacted regional and local watersheds. (Verschuren et al., 2000; Indermuhle et al., 1999; Petit et al.,

1999; Alley and Bender, 1998; Machado et al., 1997; Bond et al., 1997; Roberts et al., 1993;

Street-Perrott and Perrott, 1990). The tectonics that created the Al-Azraq Basin provide a nearly 500,000 years, high-resolution record of fluctuating paleoenvironments, which reflect these changes in climate.

Multiple proxies reflect different aspects of environmental change. Bulk organic matter and stable isotope geochemistry are useful tools to reconstruct the past environment and climate by identifying sources of organic matter (Meyers, 2003). Calcium carbonate provides information about precipitation and evaporation rates, and oxygen and carbon isotopic compositions reflect the moisture conditions of past environments (Leng and

Marshall, 2004). However, diagenesis, or post-depositional processes that alter original sediments or minerals, can affect either the organic matter (Meyers and Ishiwatari, 1993) or calcium carbonate (Talbot and Kelts, 1990).

The distributions of major and trace elements provide clear signatures of mineral formation in wet or dry climates (Martin et al., 2011). Additional methods including grain

105 size analysis, XRD, and SEM generate data supporting interpretations of paleoenvironment, paleohydrology, and paleoclimate for the Al-Azraq Basin.

Based on changes in the lithology and sediment color, the Al-Azraq sediment core

AZ1 is divided into three lithologic zones. Zone 1 extends from 1 to 31.5 meters and contains silt, sands, carbonate precipitate, and laminated massive dolomite. Zone 2 extends from 31.5 to 48 meters and silt, clays, and diatoms characterize these sediments. Finally, Zone 3 from

48 to 52 meters consists of silt, sand, and small angular chert fragments (Figure 7.1).

Figure 7.1. Diagram of the lithology of the Al-Azraq sediment core AZ1 and lithologic and climate zones 1-3.

106

Diagenesis of Organic Matter

Preserved organic matter (OM) in sediments can provide information about the

13 history of vegetation in lake sediments for millions years (Meyers, 2003). C/N and δ C values of organic matter retain information about vegetation sources for multimillion-year time frames (Meyers, 1993). However, diagenesis can play an important role in the decomposition of organic matter and thereby altering its paleoenvironmental or paleoclimatic signal. Some studies indicate degradation of organic matter negatively influences isotopic signals of organic matter (Herczeg, et al., 2001; Kuhry and Vitt, 1996; Meyers, 1997;

Sharma et al., 2005).

Organic matter accumulates in the bottom of a lake, and then it decomposes with CO2 as a final product. The effect of diagenesis on organic matter differs among the organic components, for example nitrogen-bearing organic matter decomposes rapidly (Talbot and

Johannessen, 1992). Loss of organic nitrogen takes place as a result of post-depositional decomposition of nitrogen bearing matter. Therefore, a decrease in total organic nitrogen

(TON %wt) and an increase in C/N ratios indicate loss of organic nitrogen relative to organic carbon. The loss of organic nitrogen makes an interpretation of organic matter sources for nitrogen isotopic composition unreliable. Talbot (2001) suggests if there is no influence from

15 inorganic nitrogen in sediments, the C/N ratios and δ Norg indicate the source of organic matter. Plotting %TON vs. %OC results in a linear trend with the intercept at 0.04 of %TON

(r2= 0.6452) indicating inorganic nitrogen is not present in Al-Azraq lake sediments (Figure

15 7.2a). According to Talbot (2001) this demonstrates the C/N ratios and δN org values are reliable proxies for these sediments to identify the sources of organic matter in lake

15 sediments. Additonally, Figure 7.2b shows the plot of C/N ratios and δN org values with the

107 sample outlier located at 0.18%TON and 4.36 %OC removed. In this plot the R2 decreases, but the intercept remains the same. This further supports the interpretation of no presence of inorganic nitrogen.

a .

b . Figure 7.2 (a). Plot of Total Organic Nitrogen (%TON) vs. Percentage of Organic Carbon content (%OC) demonstrating the lack of inorganic nitrogen. (b). Plot of Total Organic Nitrogen (%TON) vs. Percentage of Organic Carbon content (%OC) without sample outlier (0.18, 4.36). While the R2 value decreases (R2 = 0.414 ), the slope intercept does not change, and therefore further demonstrates a lack diagenesis in Al-Azraq sediments.

108

There are two additional indications of organic matter diagenesis affecting isotopic

13 composition signals. First, diagenesis of organic matter produces a decrease in δ Corg while the C/N ratio increases due to the effects of diagenesis on nitrogen-bearing compounds

(Herczeg et al. 2001; Meyers, 1997). In the Al-Azraq sediment core AZ1, the opposite

13 relationship is observed including an increase in δ Corg with a corresponding decrease in C/N

13 ratios, except in Zone 3. Second, a high correlation between δ Corg and C/N signals indicates alteration of OM by diagenetic processes ( Herczeg et al. 2001; Meyers, 1997: Sharma et al.,

13 2 2005) (Figure 7.3). A low correlation between δ Corg vs. C/N ratios (r = 0.2776) again demonstrates the opposite relationship between these two variables. This also indicates the absence of any influence of diagenesis on organic matter in Al-Azraq sediment core AZ1. As a result, the isotopic signatures of bulk organic matter from Al-Azraq sediment core AZ1 potentially provide reliable information about past vegetation, environments and changes in lake paleoproductivity.

13 Figure 7.3. Plot of the relationship between δ Corg and C/N ratios. It demonstrates low correlation between the ratios, indicating the absence of diagenesis of organic matter in AZ1 core sediments. Most of the organic matter falls within the range of aquatic algae with some mixing terrestrial plants. Two samples from the same zone fall within the range for C3 plants

109

Diagenesis of Calcium Carbonate

Diagenetic alteration can significantly change the oxygen isotopic composition signal of authigenic carbonate (Matthews and Katz, 1977; Campos and Hallam,1979; Dickson and

Coleman, 1980; Drummond et al., 1993). Identifying the presence of diagenesis of calcium carbonate is a complex issue and a source of continuing research (Cry, 2004). However, some approaches may be helpful in determining the influence of diagenesis on the geochemistry of lacustrine carbonates such as: petrographic or smear slide analysis, examining standard trends of carbon isotopic composition of carbonate, or comparing major element ratios to oxygen isotopic composition (Matthews and Katz, 1977).

Smear slides revealed grains of calcium carbonate with a variety of siliclastic minerals. However, some samples under polarized light showed alteration of the carbonate to dolomite (stained), which may affect the oxygen isotopic composition (Figures 5.7 and 5.9).

Another kind of carbonate diagenesis might occur due to processes of methanogenesis or sulfate reduction processes. In order to identify the impact of either one,

13 one has to examine the trend of δ Ccarb (Talbot and Kelts, 1990). When lake water is low in

13 sulfate, bacterial methanogenesis activity dominates, which causes enrichment of Ccarb values (Talbot and Kelts, 1990). However, when lake water is enriched with sulfate, sulfate

13 reduction is present as bacterial mediated processes. Negative shifts in δ Ccarb values record these kinds of processes (Talbot and Kelts, 1990). Sulfate reduction might occur in Zone 1 of the Al-Azraq sediment core (Figure 7.4). X-ray diffraction, SEM, and ICP-AES identify the presence of celestite (Sr SO4) and secondary gypsum (CaSO4•2(H2O)) in Zone 1. This confirms the presence of sulfur and suggests sulfate carbonate diagenesis occurred in Zone 1.

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However, even if there were some bacterial processes in the basin, it would not significantly impact the oxygen isotopic composition of authigenic carbonate (Talbot and Kelts, 1990).

13 18 Figure 7.4. Plot of δ Ccarb vs. δ Ocarb showing the none-effect of either methanogenesis, or the impact of sulfate reduction diagenesis of the carbonate calcium in Zone 1of the Al-Azraq core 1.

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Figure 7.5. SEM image of dolomite in Zone 1 of the Al-Azraq sediment core AZ1 (top). The EDS spectrum also indicates the presence of dolomite, showing Mg% and Ca% have peaks of similar height.

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Figure 7.6. Plots of Ca/Mg ratios vs. depth (a) and Mg% vs. Ca% (b) of the Al-Azraq sediment core AZ1. a. The dashed line shows the boundary of dolomite presence at 1.0, the red line maps fluctuation in the Ca/Mg ratio with depth; b. Mg% vs. Ca% indicating Zone 1 and Zone 3 have the most dolomite, but the clustering of Zone 2 samples near the intercept reflects the absence of dolomite in Zone 2.

Another kind of diagenesis that may impact the oxygen isotopic composition values is dolomitization by increasing the oxygen isotopic composition away from the equilibrium of meteoric water (Drummond et al., 1993). X-ray diffraction identified dolomite in Zone 1 extending from the 1 to 31.5 meters (Appendix C). In addition, the SEM revealed the presence of dolomite in Zone 1 samples (Figure 7.6). In addition, plotting ICP-AES percentages of Mg% vs. Ca% provides information about the percentage of dolomite in a sample. Figure 7.6 reveals that most samples in Zone 1 are dolomite except the samples with low Mg%, and likewise for Zone 3. However, Zone 2 demonstrated low Ca% and Mg% indicating the absence of dolomite. Moreover, the molar ratio of Ca/Mg of ideal dolomite is 113

1.0 (dashed line) (Goldsmith and Graf, 1958; Sperber et al., 1984). The values of Ca/Mg are slightly over 1 % indicating the presence of dolomite in Zone 1 and Zone 3 (Figure 7.6).

Therefore, not all the carbonate isotopic composition data are reliable for use in covariance with oxygen isotopes as an indicator for paleohydrology.

Hydrothermal fluids play an important role in the diagenesis of carbonate. Major element chemistry can determine the occurrence of hydrothermal diagenesis of carbonate

(Cyr, 2004; Matthews and Katz, 1977). Matthews and Katz (1977) indicate diagenesis by

18 hydrothermal fluid decreases the δ Ocarb values and increases the Mg/(Mg+Ca) ratios, thus

18 decreasing the correlation to Mg[(Mg+Ca)]. The plot of δ Ocarb vs. Mg (Mg+Ca) of Al-

Azraq sediment core AZ1 produced a very low correlation (R = 0.487) due to an increase

18 δ Ocarb but with a decrease in Mg (Mg+Ca) indicating the absence of hydrothermal diagenesis (Figure 7.7).

10 R² = 0.2376 8 6

4 carb

O 2 18

δ 0 -2 -4 -6 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 Mg/(Mg+Ca)

18 Figure 7.7. δ Ocarb vs. Mg (Mg+Ca) reflects a poor correlation between the chemical data.

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Mineral Weathering

Geochemical data and X-ray diffraction identified several minerals within the basin sediments. Some might be produced in the lake itself, whereas others are brought into the basin as detrital weathering products. The degree of chemical weathering can be estimated by the Chemical Index Alteration, CAI = [Al2O3/ (Al2O3 + CaO + Na2O + K2O)] *100 (Roy,

2010). The calculated CAI for AZ1 core sediments determined the degree of weathering, below 40%, to be low overall (Figure7.8).

At the same time the ratio of K/Na indicates the weathering to be high in Zone 1, low in Zone 2, and very moderate in Zone 3 (Horton et al., 1999) (Figure 7.8). This finding supports Zone 1 being a dry period with weathering associated eolian and alluvial processes, whereas, the lack of weathering in Zone 2 is compatible with an interpretation of a period of wet climate.

In addition, the ratio of Fe/Al exhibits a consistently very low ratio in Zone 1, indicating the sources of iron are detrital (Pattan et al., 2012) (Figure 7.8). In Zone 2 the fluctuations for this ratio almost double in value indicating an additional authigenic source of iron in the basin, possibly from oxidation in the lower part of the core. The magnetic susceptibility data support this interpretation in addition to identifying detrital iron sources from influx to the paleolake (Figure 5.12).

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Figure 7.8. Fe/Al ratio, K/Na ratio, and Chemical Index Alteration (CIA) vs. depth of Al- Azraq core AZ1 exhibiting a signal indicative of detrital sources of iron in the upper core sediments of Zone 1, and a mix of authigenic and detrital source in Zone 2.

Paleohydrology and Paleoenvironmental Interpretations

Interpretations of the paleohydrology and paleoenvironments of the Al-Azraq Basin discussed here are based on multiple proxies that including geochemical data, stable isotopes geochemistry of carbonate and organic matter, grain size analysis, and other supporting methods to determine environmental changes through the Quaternary Period. The

116 geochemical and isotopic proxies support the initial core divisions, based on changes in lithology and sediment color, into Zones 1, 2, and 3. The first part of this discussion focuses on paleohydrology. The main proxy for paleohydrology in Zone 1 is the isotopic composition of carbonate. In Zone 2 the low abundance of primary calcium carbonate precludes the use of isotopic composition, however, abundance of diatoms and clay minerals indicate a lake phase. Interpretations of paleohydrology for Zone 3 are complicated by the presence of carbonate diagenesis. The second part of the discussion focuses on the distribution of organic matter and its implications of paleoenvironmental change. The main proxy for paleoenvironment in Zone 1 is grain size, mineralogy, and the isotopic composition of carbonate. In Zones 2 and 3 the isotopic composition of organic matter and grain size reflect the paleoenvironment.

Carbonate Minerals

Three types of carbonate minerals identified in Zone 1 include: calcite, dolomite, and ankerite. Calculating percentages of CaCO3 provides information regarding paleoenvironmental conditions during mineral precipitation. Yu and Kelts (2000) use carbonate mineral shifts in Mg/Ca ratios, salinity, and alkalinity to infer climatic changes associated with the Late Glacial/Holocene transition. Mg/Ca ratios reflect the phases of carbonate formation (Muller and Irion, 1972, Eugster and Kelts, 1983; Scoffin, 1987). Mg/Ca ratios less than 2 indicate low Mg-calcite records, whereas Mg/Ca ratios between 2 to 7 indicate Mg-calcite, and Mg/Ca ratios of 7 to 12 are high Mg-calcite and protodolomite.

However, Mg/Ca ratios over 12 indicate the presence of aragonite (CaCO3), or possibly magnesite (Eugster and Kelts, 1983).

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Zone 1

Figure 7.9 reveals the presence in Zone 1 of dolomite and minor calcite. The ratios of

Mg/Ca range from 0.1- 1.7 in some levels reflecting the presence of low-Mg-Calcite (Figure

7.9). In some levels the Mg/Ca peaks to 3.4, reflecting the presence of Mg-calcite or dolomite (Figure 7.9). At meter 32 the Mg/Ca ration increases to 11, indicating the occurrence of High Mg-calcite and the presence of ankerite in Zone 2. X-ray diffraction then confirmed the presence of ankerite (Appendix 6).

Figure 7.9 Calcite and dolomite in the upper part of the core Zone 1, and ankerite Zone 2, and minor dolomite and carbonate diagenesis in Zone 3.

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Primary and Secondary Calcium Carbonate

Ratios of Mn/Ca and Mg/Ca differentiate primary and secondary carbonate precipitation products. Low ratios of Mn/Ca and Mg/Ca indicate secondary carbonate, whereas elevation in Mn/Ca and Mg/Ca ratios at the same time reflects primary carbonate production (Li et al., 2013). Distribution along a positive correlation of Mg/Ca vs. Mn/Ca indicates primary and secondary carbonate products. Zones 1 through Zones 3 reveal a continuum from primary carbonate products in Zone 1, to mixing of primary with a minor presence of secondary carbonate in Zone 2 and finally secondary carbonate in Zone 3 (Figure

7.10). The minor secondary carbonate in Zone 2 may result from recrystallization under oxic conditions (Li et al., 2013). The type of carbonate in Zone 2 is ankerite [Ca (Fe2+, Mg, Mn2+)

(CO3)2], identified by X-ray diffraction (Appendix C). Ankerite forms when Mg replaces iron and manganese. This finding potentially explains the source of ankerite in Zone 2 generating from authigenic carbonate.

Figure 7.10. Mg/Ca and Mn/Ca ratios indicating primary and secondary carbonate products for Zones 1, 2, and 3 of Al-Azraq core AZ1.

119

Dutkiewicz et al. (2000) identified the formation of calcite from Lake Fenghuoshan

18 in saline playa systems. The relation between δ Ocarb and Mg/(Mg+Ca) reflect the formation of calcite in saline or fresh lake waters. Both saline and fresh water demonstrate well-defined patterns. Values representing saline water follow an increasing positive trend, and fresh water

18 values cluster tightly The plot of δ Ocarb vs. Mg/(Mg+Ca) shows the carbonate in the Al-

Azraq Basin formed in saline water. This relationship further identifies the saline generated carbonate by relatively high δ18Ocarb and Mg/(Mg+Ca) ratios. These high ratio values can reflect diagenesis by hydrothermal or petrographic alteration; however, these types of alteration are unlikely in these samples as previously discussed in the diagenesis section.

Ocarb 18 δ 2

0 0 2 4 6 8 Mg/(Mg+Ca)

18 Figure 7.11. δ Ocarb vs. Mg/(Mg+Ca) indicates the precipitation of carbonate in the Al-Azraq basin from saline lake waters.

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Covariance of Carbonate Isotopes

Following on the previous discussion, it is possible to examine the covariance of

18 13 18 δ Ocarb and δ Ccarb in the meters containing calcium carbonate. The covariance of δ Ocarb

13 and δ Ccarb indicates whether a lake is an open or closed system, but only if the lacustrine carbonates are primary carbonate (Talbot and Kelts, 1990; Li and Ku 1997). R-values close to 0.9 indicate a closed-basin system (Talbot, 1990). The presence of dolomite impacts this

13 covariance because it is a secondary carbonate product and has more negative δ C values

18 than primary carbonate and large range of δ O values (Yu, 2005). Therefore, the oxygen and carbon isotopic compositions were excluded from this estimation in the meters in which the calcium carbonate is from dolomite with high degrees of diagenesis. An exception to this is a hypothesis that dolomite exposed to early diagenesis may not affect the oxygen and carbon isotopic composition. Therefore, Figure 7.12 illustrates the covariance of oxygen and carbon

121

13 18 Figure 7.12. The covariance of δ Ccarb and δ Ocarb of calcium carbonate from the Al-Azraq basin demonstrated that the basin has been a closed system throughout its history.

isotopic composition including some meters with dolomite. Plots of covariance by meter

18 13 exhibit high correlation of covariance between δ Ocarb and δ Ccarb values indicating the Al-

Azraq Basin has been a closed system throughout its history.

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Paleohydrology and Paleolake Levels

In closed-basin lake systems, rising lake levels affect the carbon and oxygen isotopic composition. If the evaporation of lake water is less than the inflow, i.e. lake water is rising,

18 δ Ocarb is similar to that of the precipitation and indicative of a wet climate (Mayer and

Schwark, 1999). However, in a dry climate where lake levels are low, i.e. evaporation is

18 16 higher than precipitation; it leads to an increase δ Ocarb values as the O is differentially

13 18 depleted. This situation results in increases in the δ Ccarb and δ Ocarb values (Li and Ku,

13 1997; Mayer and Schwark, 1999; Dean and Schwalb, 2000). The reason δ Ccarb values increase during high evaporation and low water input is photosynthetic processes

12 13 differentially remove light carbon ( C) resulting in an increase δ Ccarb values. In addition, the partial pressure of CO2 increases with a strong increase in evaporation and this further

12 facilitates the uptake of C (Li and Ku, 1997). Therefore the degree of variance between

13 18 δ Ccarb and δ Ocarb values can indicate lake water levels. The values of carbon isotopic composition are smaller than the oxygen isotopic composition of carbonate and both are

13 depleted during periods of high precipitation. Conversely, increased values of δ Ccarb and

18 δ Ocarb indicate episodes of higher evaporation and lower lake levels (Li and Ku, 1997).

Paleoenvironmental Zones

13 18 Based on changes in δ Ccarb and δ Ocarb values, variation in chemical element concentrations, and X-ray diffraction data, AZ1 core sediments divides into three zones.

Zone 1, relative to Zone 2, represents a drier lake phase transitioning to seasonally mixed

123 eolian and alluvial inputs at the top of the core. Zone 1 contains six subzones 1a, 1b, 1c, 1d,

1e, and 1f). High clayey silt sediments and calcite characterize Zone 1a, which extends from

18 the surface to 1 meter (Figure 7.13 and Appendix C). Plotting δ Ocarb values and Mg/Ca ratios indicate the presence of carbonate from different sources (Li et al., 2013) (Figure

18 7.14). Based on the δ Ocarb values and Mg/Ca ratios the source of calcite in this first meter

(Zone 1a) is both detrital and authigenic (Figure 7.14). Zone 1a represents eolian and alluvial deposits potentially transferring sediments including calcite. Calcite could potentially transfer into this area from the surrounding playa, or it could precipitate from calcium- rich flood waters during the winter season. There is an absence of dolomite.

Zone 1b extends from 1 to 3.30 meters and is transitional between the surface and

18 Zone 1c. During this time calcite occurs with minor dolomite. The δ Ocarb values indicate an overall balance between precipitation and evaporation. Fluctuations in lake level correspond with a spike of clay and coarse silt supports this idea (Figure 7.13).

18 Zone 1c extends from 3.30 to 11.65 meters. The δ Ocarb values are more positive and

XRD reveals changes in calcium carbonate from calcite to 86.9% dolomite as well as the presence of illite and hematite (Appendix C). Sandy silt deposits are abundant (Figure 7.13).

Talbot and Kelts (1990) suggest sediment deposition with the presence of dolomite reflects

18 low lake levels and probably high salinity. Therefore, Zone 1c δ Ocarb values support increased evaporation greater than precipitation, low lake levels, and possibly high salinity.

Grain size analysis of clay, silt, and sand reveal an increase in sand percentage over silt and clay supporting the interpretation of high evaporation and low lake levels (Figure 7.13). The

124

Figure 7.13. Carbon and oxygen isotopic composition of carbonate and grain size analysis identifying periods of dry and wet climate and low and high lake levels of Al-Azraq sediment core AZ1. Yellow zone represents eoline deposits as a result of wind activity. Blue zone reflects wet climate with increasing the precipitation, and light brown zone represents dry climate.

18 presence of hematite also supports a dry climate during this zone. The high values of δ Ocarb

13 and more negative δ Ccarb values suggest the presence of diagenetic carbonate by

125

Figure 7.14. Mg/Ca ratio vs. oxygen isotopic composition of carbonates illustrating the source of carbonate in the Al-Azraq sediment core AZ1 in Zone1.

bacterial sulfate reduction (Talbot and Kelts, 1990). Therefore, the dolomite may be formed in this reducing environment and preserve the isotopic composition record of the water.

Zone 1c also contained celestite (SrSO4), a strontium sulfate, at meter 4. The XRD showed 74.4% celestite, 17.4% dolomite, and 8% iron. Additional SEM observation included visible crystals of celestite (Figure 7.10). Barium (Ba) that occurs in dolomite or dolomitic limestone is interchangeable with strontium and can also lead to celestite. This mineral resembles barite but it is less common (Anonymous 1). The Sr/Al peak at the beginning of meter 4 coincides with the presence of gypsum (CaSO4•2 (H2O)) (Appendix C) during high salinity and when carbonate is not precipitated. The absence of carbonate indicates the formation of celestite as Sr sulfate (Martin et al., 2011).

126

Figure 7.15. Percentages of clay, silt, and sand from Zone 1c (a) and 1d (b). a. High percentages of sand over clay in Zone 1c support low lake level interpretation. b. In Zone 1d the reverse conditions with high percentages of clay over sand support interpretation of high lake level.

127

Figure 7.16. SEM image, and XRD and EDS spectra of the strontium sulfate mineral celestite from meter 4 of the Al-Azraq sediment core AZ1.

Zone 1d extends from 11.5 to 12.5 meters. The lithology in this section changes to more clay and fine silt and the XRD identifies the presence of 60.7% calcite and 1.9%

18 dolomite (Appendix C). The δ Ocarb values are more negative indicating a change in the environment from a dry to a wet period. The increases of clay particles associated with more

128 negative oxygen isotopic composition of calcite support the interpretation of increasing lake levels in this zone. Fe, Cr, and P concentrations also increase in this zone, which might be washed from the catchment into the paleolake, also supporting a wet period for this zone

(Figure 7.13). P is a significant element in primary production and its increase in concentration signifies an increase in lake primary productivity (Hickey and Gibbs, 2009).

Also, smear slides showed the presence of possible foraminifera (Figure 5. 7) and a low abundance of diatoms. The formation of calcite raises pH in many lakes (Martin et al., 2011).

Thereby, diatoms were exposed to dissolution in this zone.

Zone 1e extends from 12.5 to 14.5 meters and laminated carbonate characterizes this section of the core (Figure 5.2). X-ray diffraction identifies the presence of dolomite, minor calcite, and muscovite (Appendix C). The presence of muscovite indicates the increase in the weathering activity that brought it from the catchment to the lake. Lake level is low due to the presence of dolomite (Talbot and Kelts, 1990). Additionally, grain size analysis revealed

18 high concentrations of coarse-grained silt and fine sands. During this period the δ Ocarb signatures indicate an increase in evaporation over precipitation and this zone is considered to be a drier period.

Zone 1f extends from 14.5 to 18 meters and represents a period less dry than the

18 previous Zone 1e due to the less positive values of δ Ocarb that ranged from 2 - 4. Dolomite, halite, and quartz are present in this zone (Appendix C). Lake levels fluctuate in this zone on the basis of oscillations in sand, silt, and clay particle sizes. In the last two meters of this zone clay dominates sand. This suggests the last 2 meters of this zone represents a major

129 transition bed between Zone 1 and Zone 2. A spike of sand particles to 80% at meter 25 potentially indicates a heavy storm event during Zone 1f (Figure 7.12).

Paleoenvironment and Paleoproductivity

Zone 2 extends from 31.5 to 48 meters and differs from Zone 1 with a marked increase in the abundance of clays. Organic matter present in this section enables analysis of carbon and nitrogen isotopic composition. This method is becoming widely used in paleoenvironmental research because it is reliable, particularly in areas where preservation potential of organic forms is low. On the basis of carbon and nitrogen isotopic composition of organic matter and stable isotope geochemistry core AZ1 sediments divide into four subzones (2a, 2b, 2c, and 2d) (Figure 7.17).

Figure 7.17. Carbon and Nitrogen isotopic composition of bulk organic matter with results of grain size analysis. Show climate Zones 2a, 2b, 2c, 2d and Zones 3a and represent wet climate, whereas 3b reflect dry climate.

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Zone 2a represents a long period lake environment extending from 31.5 to 41.80 meters. This zone is represented by the longest continuous sediment of core AZ1 and contains meters of rhythmites of light (diatoms) and dark material. Organic matter in this zone is low. C/N ratios are good indicators for the source of organic matter (Altabet, 1988; Matson and Brinson,

1990; Thornton and McManus, 1994; Cifuentes et al., 1996; Nakatsuka et al., 1997; Goñi et al., 1998; and Graham et al., 2001). C/N ratios between 4 and 10 reflect authigenic lake organic matter (Meyers, 2003). Algae utilize dissolved inorganic nitrogen (DIN) in the form

- of NO 3, whereas, plants use atmospheric-derived N2 (Peters et al., 1978). The nitrogen isotopic composition of organic matter ranged from 5‰ to 7‰ indicating the source of organic matter is aquatic algae. In addition, the carbon isotopic composition of organic matter values range from -20‰ to -24 demonstrating the presence of aquatic organic matter (Figure 7.18 a and b). As a consequence, this period represents a wet climate and a high lake stand (Figure 7.17).

Nitrogen isotopic composition values vary throughout the lake ranging from 4‰ to

7‰ indicating changes in lake productivity. In the beginning of Zone 2a, high productivity occurs simultaneously with a peak in P%. The percent of phosphorous decreased with the decrease in nitrogen isotopic composition values. Diatoms are extremely abundant in this zone comprising a majority of the sediment matrix, but the frustules are highly broken

(Figure 5.10). The high abundance of diatoms also indicates a high lake water stand in this period. Major and trace element analysis recognizes high concentrations of Na, and XRD identifies the presence of halite (Appendix C) in this zone indicating a saline lake.

Zone 2b extends from 42.42 to 43.37 meters. The organic carbon content increased slightly with an increase in the C/N ratios ranging from 7 to 10 (Figure 7.17). This finding

131 reflects a slight increase in paleoproductivity slightly in this zone (7.17). The carbon isotopic composition which ranged from -23‰ to -24‰ also supports a wet climate for this period.

Zone 2b is also a high water lake with increased diatoms abundance. The diatom frustules in this zone are more intact than Zone 2a. The presence of sodium chloride indicates again the lake water is saline and the source of organic matter is aquatic algae (Figure 7.18 a. and b.).

Zone 2c extends from 43.37 to 44.86 meters. In this phase of the lake, the organic content decreases ranging from 0.4% to 0.5% and C/N ratios are between 7 and 8. Additionally, the nitrogen isotopic composition values decrease ranging between 4 and 4.5. The organic matter in Zone 2c is aquatic algae as reflected by more negative values of carbon isotopic composition and C/N ratio (Figure 7.17). However, low values of nitrogen isotopic composition and low organic content low point to low productivity (Figure 7.18 a. and b.).

Therefore, this period of lake represents a wet climate with low productivity (Figure 7.17).

Zone 2d extends from 44.86 to 48 meters. The C/N ratio ranges from 8 to15 with increasing organic matter content ranging from 0.4% to 1.17%. However, nitrogen isotopic composition values again decrease slightly from 3‰ to 4.5‰, whereas carbon isotopic composition values are -23‰ to -21‰. These findings reflect the composition organic matter is mixed aquatic algae and land plants (Figure 7.18 a and b). The nitrogen isotopic composition of organic matter values decrease slightly supporting an interpretation of input of land plants to the basin (Figure 7.17 a and b). Moreover, magnetic susceptibility values from meter 45 also increases suggesting an influx of detrital material from the catchment

(Figure 5.12). As a result, this zone of the lake represents a transition and mixing zone in a wet climate characterized by high organic and mineral influx to the lake from the catchment

(Figure 7.17 and 7.18 a and b).

132

10 9 8 7 + Zone 2a .;. 6 I Zone 2b z 5 • AZone 2c 4 land Plants '" 3 XZone 2d 2 CAM )t:: Zone 3a 1 0 . 20ne 3b -28 -25 -22 -19 -16 a. 613C %0

10 r-----~------~ 9 • 8 7 + Zone 2a .;. 6 . Zone 2b z 5 • . Zone 2c iO 4 3 X Zone 2d 2 X Zone 33 1 . Zone 3b 0+---~---~-----1 o 10 20 30 b. (IN

Figure 7.18. (a.) δ15N ‰ vs. δ13C ‰ and (b.) δ15N ‰ vs. C/N ratios illustrate different sources and types of vegetation in the Al-Azraq sediment core AZ1.

133

Zone 3 extends from 48 to 52 meters. Lithology divides this zone into Zone 3a and

Zone 3b (Figure 7.17) . Zone 3a extends from 48 to 49.35 meters. C/N ratio increases in this zone ranging between 9 and 27, whereas the organic matter content ranges from 0.5 to a high of 5. This is the highest organic matter content in core AZ1 and suggests the increased organic matter is of terrestrial origin and supports an interpretation of increased precipitation

(Figure 7.18 a and b). However, the values of nitrogen isotopic composition of bulk organic matter also indicate the presence of aquatic organic matter (Figure 7.17 a and b).

At the beginning of Zone 3a specifically from 48 to 48.15 meters, yellow deposits occur with a very strong sulfur smell. SEM and ICP-AMS identify the presence of sulfur

3+ (Figure 7.19). Additionally, XRD identifies the presence of jarosite (KFe 3(SO4)2(OH)6), hydrous sulfate of potassium and iron (Figure 7.19). It is a secondary mineral forming from the oxidation of sulfide-bearing rock. Pyrite (FeS2) occurs in this section (7.19) also indicating the formation of jarosite was from sulfide-bearing sediment.

Zone 3b lithology changes completely from soft sediments to very compact, massive dolomite sediments identified by XRD and smear slide observation. The carbon isotopic compositon values are not reliable for sourcing organic matter in this zone due to the presence of diagenesis. The high correlation of C/N ratios vs. δ13C‰ (R = 0.818) indicates

13 the presence of diagenesis which impact δ Corg‰ values (Figure 7.20). The lithology of

Zone 3b indicates an arid period of high evaporation to precipitation, but the high correlation of C/N ratios vs. δ13C‰ seems to indicate great C3 plants and thereby higher moisture.

Given the lithology this interpretation is unlikely and therefore an indication that diagenesis has overridden the vegetation signal.

134

Jaros/I', 11"- KF'j(S0J;(01I)

I 1

•

Figure 7.19. SEM image, XRD pattern, and EDS spectra identifies the presence of jarosite 3+ (KFe 3(SO4)2(OH)6), hydrous sulfate of potassium and iron in Zone 3a.

135

16 14 R² = 0.6703

10 8

C/N ratio C/N 6 4 2 0 -25.00 -24.50 -24.00 -23.50 -23.00 -22.50 -22.00 13 δ Corg

13 Figure 7.20. C/N ratios vs. δ Corg indicates the presence of diagenesis in Zone 3b of Al-Azraq sediment core AZ1.

Summary of Paleoclimate Implications

While the modern climate in Jordan is arid to semi-arid, stable isotope geochemistry, including carbon and nitrogen isotopic composition of bulk organic matter, indicate long periods of higher than present moisture and episodes of extensive evaporation. The sediments demonstrate a pattern of marsh, lake and eolian deposition. The sediments begin with a marsh in Zone 3 transitioning to a deep water lake in Zone 2 indicative of significant increase in moisture. Abundant aquatic and terrestrial organic matter characterizing the Zone 2 lake phase also reflects this significant increase in precipitation. Multiple cycles of shallow water and carbonate deposition characterize Zone 1. They demonstrate a significant shift in climate patterns. Precipitation is still clearly available and accumulating as a shallow lake, but punctuated, potentially seasonally, by intense carbonate forming evaporation. Late

136

Pleistocene and Early Holocene sediments are missing and may represent a dry, erosive phase.

Other examinations of paleoclimate from Al-Azraq marsh sediments at the lakeshore

(Azraq as-Shishan area and Azraq ad-Duruz) infer fluctuations in lake levels and shifts in precipitation for the last 150 ka years (Jones and Richter, 2011, Ames and Cordova, 2012,

Cordova et al., 2012). Similar to AZ1 sediment, throughout this area evidence of deposition during the Pleistocene-Holocene transition is missing and interpreted to be dry, with the marshes only returning in the Late Holocene Roman era (Woolfenden and Ababneh, 2011).

These marsh sections overlap in time with the upper sediment from the basin interior

(Davies, 2000; Ahmad, 2010, Ahmad present study). However, the lower cored sediments of

AZ1 extend to potentially 600 ka years and, at present, have no shoreline equivalent.

From the discussion of paleolake chronology in Chapter 3, it is known that a paleolake existed off and on in the Al-Azraq basin from the Middle to Late Paleolithic and into the Early Holocene. Evidence from other locations for regional wet phases over the last

150 ka years include: lakeshore deposits from the Nafud desert in Saudi Arabia during the final the humid phase of MIS 5 (Petraglia et al., 2011); lake shorelines from Qa el-

Mudawwara (Abed et al., 2000); and speleothems from Hoti Cave in Oman (Fleitmann et al.,

2003) and Peqiin Cave, Northern Israel (Bar-Matthews et al., 2008).

Older climate correlations beyond MIS 5 to the lower lake sediments of the Al-Azraq exist beyond the basin. Abed et al. (2000) report lake high stands from Qa el-Mudawwara between 152 and 170 ka associated with MIS 6; and a δ18O‰ record from Hoti Cave speleothems in Oman, record a wet period between 180 and 200 ka or MIS 7 (Fleitmann et

137 al., 2003). Abed et al. (2008) correlates 330 ka year old lake sediments from Umari, just south of the Al-Azraq basin, to MIS 9.

The most relevant correlations in age are the oldest Dead Sea exposures of Lake

Amora deposited between ~740 and 70 ka years (Torfstein et al., 2009). The extensively dated stratigraphic section encompasses MIS 18 to 5, the period most nearly represented by the lower Al-Azraq lake sediments. Torfstein et al. (2009) interpret the oscillations of Lake

Amora to being similar to Lake Lisan and Holocene Dead Sea processes with wet phases occurring during glacial periods and more arid conditions associated with interglacial periods.

From the western Mediterranean, Rodrigues et al. (2012) identified wet phases from

570 to 300 ka, encompassing MIS 15 and 9, with eight Heinrich-type events of extreme cold temperatures punctuating a general deglaciation trend similar to the Last Glacial Maximum.

These may correspond to AZ1 Zones 3 and 2.

The paleoclimates represented by Al-Azraq AZ1 sediments can be interpreted in several ways. In close proximity to AZ1, and most likely hydrologically linked, are the Azraq spring sites. Cordova et al. (2012) interpret MIS 5e and MIS 1 to be extremely arid. They point out that high moisture signals in the marshes may be a result of the strong aquifer flow as opposed to actual increases in precipitation. They state the occurrence of highest moisture to be during MIS 5c-a and MIS 4, the transition phase from the last interglacial to glacial period. Climate reconstructions for the Dead Sea (Torfstein et al., 2009) also show glacial periods to be wet and interglacials arid. This potentially correlates to the wet phase identified in AZ1 Zone 1 (Figure 7.21.). The AZ1 IRSL ages do not support this correlation of high moisture occurring at 24 ka and 250 ka.

138

SPECMAP δ18O MIS Lithology Climate Chronology Zones 1 IRSL 24.2± 2.0 ka 5a IRSL 163.3 ± 11.7 ka 5c 14C 11,460 BP 1 5e IRSL ˃250 ka

11 2

13 ? 15 3

Figure 7.21. Comparison of SPECMAP stacked ocean δ18O‰ record (Imbrie et al., 1984) with AZ1 lithology, climate zones, and sediment chronology following the paleoclimate interpretations of Cordova et al. (2012).

However, speleothems in northern Israel (Bar-Matthews et al., 2003), and the Eastern

Mediterranean (EM) sapropel record (Kroon et al., 1998) are well correlated and reflect strong moisture during interglacials for the production of sapropels and speleothems. The

δ18O‰ record from AZ1 correlates well with Peqiin Cave δ18O‰ record of speleothems in

Northern Israel for the period 250 ka to the present (Figure 7.22). Both potentially reveal strong wet phases for MIS 5e (Bar-Matthews et al., 2008). However, Cordova et al. (2012) state this MIS period to be extremely dry in the uplands and desert interior.

139

There continue to be disjunct regional interpretations of wet/dry phases of the paleoclimate from desert interior to Eastern Mediterranean, and inverse moisture between north and south latitudes. While the Al-Azraq AZ1 core provides valuable high-resolution biogeochemical data reflecting significant changes in past climate, it cannot yet resolve the spatial debate without more resolved chronological control.

AZ1 δ18O‰

Figure 7.22. Comparison of δ18O records from Al-Azraq AZ1 (on the left) and Peqiin Cave speleothems (on the right) plotted against time (Bar-Matthew et al., 2003) and possible correlations following the paleoclimate interpretations of Torfstein et al. (2009).

140

CHAPTER 8

CONCLUSIONS

This sediment core is the longest continuous sediment record for the upland plateau and provides the only high resolution record of paleoenvironment. Biogeochemical analyses characterized the types and sources of organic matter, indicated change in lake levels, and identified diagenetic processes in the Al-Azraq Basin, Jordan. Until this research, detailed paleolake conditions were unknown mainly due to the lack of preservation of organics and macrofossils in the deep basin sediments. This research demonstrates the presence of a deep- water lake and several periods of higher than present moisture in the Al-Azraq Basin. Based on data variations from multiple methods, the core was divided into three zones with additional subzones. Zone 1 and its subzones (1a, 1b, 1c, 1d, 1e, and 1f) are predominately arid with slight seasonal variations. Zone2 represent the transition from marsh to high stand of the paleolake (2a, 2b, 2c, and 2d) and Zone 3a is a marsh deposit and 3b is dominated by dolomite, the arid base of the cored sediments.

Summary of Findings by Zone

Zone 1

 Carbonate deposits dominated as a result of high evaporation over precipitation,

 Diagenesis of carbonate occurred throughout this zone indicated by presence of

sulfur reduction processes,

 Short period of higher precipitation in Zone 1d represented by high concentration of

clay and more negative oxygen isotope values, and

141

 Low lake levels dominate zone 1, except in Zone 1d.

Zone 2

 Increase paleoproductive indicated by the abundance of OM,

 Source of organic matter from aquatic algae and terrestrial plants,

 Diatoms dominate in this zone,

 Increase in precipitation and high lake levels, and

 A wet climate.

Zone 3

 Marsh deposit indicated by high organic matter, and

 Base of core returns to dry period with the presence of dolomite and diagenesis of

organic matter.

Mineralogical findings identified three types of carbonate including: calcite, dolomite, and ankerite. Carbon isotopic composition of carbonate identified sulfate diagenesis in most samples throughout the core sediments. In addition to the common minerals occurring in the basin, quartz, illite, kaolinite, halite, gypsum, and microcline, a

3+ ,dditional minerals identified are celestite (SrSO4) a strontium sulfate and jarosite (KFe3

(OH)6(SO4)2), a hydrous sulfate of potassium and iron.

The sediment chronology for the AZ1 sediments includes three IRSL and two radiocarbon ages from the upper most sediments, and first reported by Davies (2000), is preliminary. This work contributes to the correlation of sediment ages to the oxygen isotope record for the first 32 m, generating a record which can be compared with nearshore marsh deposits and regional climate reconstructions. The upper playa lake correlates to MIS 5 to

MIS 4. While the lower sediments remain undated, from the oldest minimum IRSL age of

142

250 ka years at 11 m, a significant age can be assumed for the lower sediments. Two ages of near the basin suggest the basin age could be between 300 and 600 ka years.

There are now multiple paleoclimate records from surrounding the the Al-Azraq and regionally for the Middel to Late Pleistocene. However, the Al-Azraq high resolution sediments are the only continuous long record for the upland and desert interior. The upper

AZ1 sediments reflect a moist phase for the transition from the last interglacial to glacial similar to those reported from Azraq ad-Duruz and Azraq as-Shishan, but it is out of phase with 'Ayn Qasiyya. However, regional records from eastern Mediterrsanean and Israel record wet glacials and arid interglacials. The AZ1 oxygen isotope record for the last 150 ka matches very well with these records. The apparent disjunction in moisture phases between some upland records and the eastern Mediterranean may be real, may be the consequence of a lag between higher Mediterranean moisture and the upland rainshadow, or as suggested by some, the effect of high spring discharge in the Al-Azraq creating the appearance of a wet phase.

The strong correlation between the upper AZ1 sediment record and regional paleoclimate records, suggests the lacustrine sediments of the lower core are equivalent to the

Dead Sea precursor, Lake Amora. The Al-Azraq is the only long continuous sediment record from the uplands comparable to this early stage of the Dead Sea. Additional age control of the lower sediments will define the chronological boundaries for the equivalent of the Dead

Sea Lake Lisan. Clearly the integration of a suite of biogeochemical approaches has greatly expanded the knowledge of the Al-Azraq basin sediments, paleoenvironments, and its links to regional paleoclimates.

143

GLOSSARY

‰- unit of measurement, parts per thousand C3- Carbon 3 photosynthetic pathway C4- Carbon 4 photosynthetic pathway CAM- Crassulacean Acid Metabolism photosynthetic pathway CAI- Chemical Alteration Index DIC- Dissolved inorganic carbon DIN- Dissolved inorganic nitrogen ICP-AES- Inductively coupled plasma atomic emission spectroscopy MASL- meters above sea level MIS- Marine Isotope Stage OM- Organic matter SEM- Scanning electronic microscopy SPECMAP- Mapping Spectral Variability in Global Climate Project, a stacked set of O18 records from ocean cores. The standard for global climate comparison TOC- Total organic carbon TON- Total organic nitrogen XRD- X-Ray Diffraction

144

Appendix A

Borehole Logs

145

Legen d

.. - .. _.. .. - ..--- .. l

Silt Dolomite

.-~ .-.- ; ...... -." ',". ".. .;....:,..:~ . ~. . ."• ' ...... • '.- "0'" . ' --. .. si lty sa nd Ca lcite

146

Sediment Core lithology Description

eoline depositions

Clayey Silt

Some detriatal carbonate (dolomite)

Clayey Silt

carbonate (dolomite)

Silt with dolomite

Clayey Silt with dolomite

147

Sediment Core lithology Description .. - .. - .. 00 Clayey Silt ..002 ..-.- Z White deposits ··Z··7.:•• •• •• on the cut sur- 0"L0oT face of the core •• •• •• (dolomite) oo Zo07.0 •• •• •• ·0r:.0oT - .. .. 4 1.-..- 00~r: .. .r- .. 7. .. Celestine · _ .. . . mineral deposits

- .. .. - .. Clayey Silt "LooT with dolomite 5 - ...... - .. - .. or:. oOZoo · - .. .. Clayey silt 0 with dolomite or:.- ..007. .. ·.. _ .. _ .. Silt with dolomite 6

148

Depth Sediment Core lithology Description 1m)

Sandy Silt with dolomite

Silt

Sandy Silt with dolomite

149

Sediment Core Lithology Description

Clayey Silt with dolomite

Sandy Silt with dolomite Sandy sat with dolomite

Fragment

Sandy Sill with dolomite

Oayey Silt with Calcite

150

Core Sediment lithology Description •• Clayey Silt with calcite

151

Sediment Core Lithology Description (m)

Sandy Silt

with dolomite

u_ eo_ •• Clayey Silt "-.. - ..•• -0- .. • .. - .. - .. with dolomite .. - .. - .. 17 .. - .. - .. .. - .. - .. .. - .. - ..

• Sandy Si lt • • • • • • • • • •• • . ~. .- " ~ .. with dolomite •• • • .. "..-- -..: -:: • • 18 • • • • •

152

Depth . (m) Sediment Core lithology Descri ption r-.~-r.-:r-----j .. •• ..>;"':1 Sandy Silt • • ...=.... • • • •• · i.. . : with dolomite 0' .,. .' ·• •..' ...=....• • • .. - .. - .. .. - .. - .. Clayey Silt 19

. , · . .. .'~., . ..- .. y...... - ·.'+.. . " ...... : . .,• .: Sandy Silt '7j• •.. • • • • • • ., ....!.. • • • •• • • • with dolomite ' 20 . ' · ... ~. ... .'1o.• •.. • ·t·.. • ....!... • _• . . .:. ..• • • • • ' . ,· ': ~. ... '1.' l :..: ... -" . ·:t: " . . . .' ---.. - ..._- - .. Clayey Silt

153

Lithology Descripthion 1m) Sediment Core

u_ •• •• _u Clayey Silt .. - ..

•• • • • ...!... •• • •• _'0 • • • • • • • • ':':;";",.- ... • • · . "-• •": .. ··:~·~I • •• , ....!.. Sandy Silt ..• •" .- • • with dolomite 22 " '. • • o..!.... • • • • • • ••• • • • • •• • • • • -· '. . • •. o..!.... , . • •• •• • • • ·,:.;... ·1 Sandy Silt .-• • • '. • • "- • • • • with dolomite •• • • • • • • .' .-• • '. · .. , ':." f '',;:~;::1 .-· . '. ~~::I • • ·o..!... '. • • . , . • • •• •• • • •

154

1m) Sediment Core lithology Description

Silt with dolomite

24 .. - .. - .. .. - .. - .. .. - I .. - I .. .. - .. - .. Clayey Silt ..·· r_u_··-r .. .. - .. _ .. 25 ..... _... .. •",. ' "I: . , Silty Sand ::.s·-'"),. ' l with dolomite

26 Silt with dolomite

155

Section 27-31m recovered only 10 cm of sediment and therefore is not represented here.

156

lithology Description

.. - .. - .. Clayey Silt .. - .. - .. .. - .. _.. .. - .. - .. .. - .. _.. .. - .. _.. .. - .. - .. .. - .. - .. Clayey Silt .. - .. - .. .. - .. - .. .. - .. _.. .. - .. - .. .. - .. - .. .. - .. - .. Oxidation .. - .. - .. .. - .. - .. .. - .. - .. .. - .. - .. .. - .. - .. Clayey Silt .. - .. _.. •• _ •• _u .. - .. - .. .. - .. _.. Oxidation .. _ .. _.. .. - .. - Clayey Silt .. - .. - .. - .. -

00-

157

1m) Core Sediment lithology Description .. - •• .. - •• Clayey Silt .. - •• Organic Matter .. - •• Diatoms .. - ••

" ' ~:.. ". ',', '.--L-. • • - 0'. · ~ -"" · ..' ...... -' ... ~... .. Sandy Silt ·'. '..., • r-"'-" • • .· - ., .. • • • • • • Diatoms •• • .-• • oS'• • ',_.': ) Organic Matter • • • .' .:. '.".' ~., • • • .- " . '. '. • r-"-" ~'. ·· ., . • 35 ...... ' ~., . • • • .-','," ...... :... ·• • • . • • • • •• • • • • .. - .. Clayey Silt .. - .. .. - .. Diatoms .. - .. 36

158

lithology Description .. - , Organic Matter Diatoms • •• • • Sandy Silt Oxidation Organic Matter Diatoms 37

Sandy Silt

Organic Matter Diatoms

38 • • • • • • Clayey Silt Organic Matter Diatoms

Sandy Silt

Organic Matter Diatoms 39

159

Depth Sediment Core Lithology Descri ption (m)

" .. ~.: " " .---- .. ~. .. .~ .. Sandy Silt .~" " •• -.a..-" • •• • • .. .- : .. -.. Diatoms ..-... : ~ .. • •••...... ~- Organic Matter • . :...-. .,..&. .-. " "• " • -"- • • " • " .. -- . .. -- .. -- . .. - .. -- . -- -- 40 ...... -- .. -- . .. -- .. --. -- -- ...... Clayey Silt .. -- .. -- .. .. -- .. -- .. Diatoms .. - .. -- .. Organic Matter 41 .. - .. - .. .. -- .. .. -- .. .. -- .. .. -- .. .. - .. -- .. .. - .. -- .. .. - .. - .. 42

160

Sediment Core Lithology Description 1m) --- -- ... - -. Matter

Silt

Matter

43 :- ... ' . • . ' '. . ~: . •• • .-',', .,...-- . ...:....." .-- • 0'. I Soody Silt .. , . • • • • • • • • • • .:... . : .-:-":. : '. .., • ....!.... •• - .', . ~::· I C)c,''','' Matter · .,• • • . • . • . • • • · :~.:.' . • • .-'. '. . 44 •• .....!...... •• :~~~ I .. · .... . _...... - . . , ' .. ~., Silt " ~.' .-',', . • • • .• - , • ...!-. • ••.::... •• ... •:'!'.:.: • • · " '..., ...... II C)c,'''';,''~'",'' • .o...!.... ., •• . _ . • • • • . • ••• " " • o...!...., •• 4S .. . • • •• •• • • •

161

Sediment Core lithology 1m) Description

• • • • • • Sandy Silt •• • • • ....!.... ••· -- · ., . • • • -• • Organic Matter · :~.'. .. .-•••• .. • :·:·~:·~ I Diatoms • • .· - ., .. • .' • '. I •• . , .: ~., ..,.. ' ·-· ...... _ ..- • • • ~ . . ... , · ': .. Sandy Silt •- • • •• . • • • • .-., . • Organic Matter · • • • . • • • • • · :~..'. .- • •• Diatoms ·· '. ..:::::~. • , L.." ••, • • · , • . • •• , ." , ...... • • -·· '. ... :::::.::1 • L... Sandy Silt • • • •• • •• •• • · , . • • • : ~'. • • Organic Matter .- :~·~I ,• .. • " •• ....!...... , ., , • Diatoms •• • • .. , • • •• ,- ·" :-':: 1 ', . , ...... !.... • • • •

162

Depth (m) Sediment Core lithology Description ---_. Clayey Silt Jarosite ------_.---.- Organic Matter " ..- : . . , .:...... _., .. ' '.- :. '~~ ,: I • • ·. - , . -.'. . . , · ':'. _., " . Sandy Silt ' •-• • ..;.-'.,.. I 49 · . ·• ~.•• Organic Matter • '. '. '. .- • • :~~~ I · ., -.' . ·- • • • • • • • • • • • • • Sandy Silt .• •• -· '. . •· .....=...... • '::'j: Dolomite • • 50 · . Organic Matter •...... =.... , . • •• •• .f.i. '. / . .• • ..,....!....• • • ....1' • "~ .: Sandy Silt ·". '... " Dolomite ::1:': '.'" :J~" " .~.. - " .' Organic Matter :t r...,:,:.·. . ::::' . ~ I • ••

163

Appendix B.

Grain Size Data and Classification

164

_ Y Y CLAY CLAY ~ L\ IIEPARD C SILTY SILTY SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SilT SilT SilT SilT S CLAYEY CLAYEY CLAYEY CLAYEY CLAYEY CLAYEY CLAYEY CLAYEY CLAYEY CLAYEY CLAYE CLAYEY CLAYEY CLAYE _ [) fOLK MUD MUD MU MUD MUD MUD CL\SS SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SilT SilT \ 1 8 $017 .92\1 4 2 ~ flers. A SptCir.r 8961.403 9945.015 Su 10356.4+1 12424.(01 1292 18153.2.iO 11624.111 10701.1 12729.778 11626.661 129·11556 11109.170 16342.148 1I791JJO) 1I4QIJ556 11615.458 11&59542 11034.89 11406.139 18m.m 26052.014 2561 70 52 51 1 1 .2 .500 5 3.M3 5.151 23.988 23.483 20.153 25.Ml 37.565 35 39. 50.646 "663 1&.811 19.861 18.258 18. 10.78) "'" 27.~ 4.1.590 46.830 45.364 4 4 2 4 7 '" .44 d50: d90: 3.623 9.765 9.861 9.195 9.380 5.106 6118 )'" 8.682 6 "64 .. W9 IS.1l41 IUSl 10.01 10.313 10.259 12.1S'! 12.113 12.101 10.'») 88 ,4 .072 dlO: 1.4\17 1.872 1.892 1.141 1.131 1.%4 "" I.m IN 2.078 2.400 2.116 2254 2189 2156 2539 2313 2 2 0.946 0.954 1.91ll 1 56 128 191 )64 939 696 86 145 , , , , , , H4 2\l 978 191 233 .4 , , , , , , 5 8 4 H21 J.531 5327 5 5 8 S "" 4.435 4.426 4 6121 6 6 "" 11 11 14 10.548 1 1 1 Kunosi!: I I 1.965 1.65 1.170 1.9!1 1.9n 2.635 W 2.0n 2.112 2.123 2.128 2.055 2.164 2.306 2.963 2.496 2.302 2.682 )998 )"" 3.171 3539 ktllless: S 4 619 C.V. 81. 95.831 91.132 96.828 82.631 88.833 91.m IOSJ.l9 105.1)6.1 11JJ.02 126.6/13 106.908 112.850 106.600 111.078 134.163 117.108 100.918 118.033 120.650 115322 12)3.]] 1 : 7 5 8 cr 1 56 44 061 957 050 622 '») 836 ,4 , , , , , . 3351 6 1 1 Q.i 97.m arUlD BU lJ2356 111.&42 187 109529 1 m.917 43l. 426300 21\4 4 259100 272.811 231569 4 308.733 344 380 338375 663.45 3 ' 183 \ 3 43 4 512 417 486 6 .703 , , . 1. 1 17.601 12.665 13.513 16.153 16.776 18.206 10.259 11.918 10.246 11.906 17.239 1 Men: 24.428 20.441 10.206 \ I 1 80 179 "" .. _. 28 .m 1.911 I. 1.965 4. t>l5 WI 2.918 2.032 2.4 J.lO 4'" 0.Q28 2 0.114 0.601 0194 3.10 0.1" 3 8.613 '''' , , 4 9 1 1 53 89 123 144 107 118 228 9 863 Silt ,4 ,4 , , , , , , . % '4644 411 41379 )5 72.127 70 73.SSO 6/1 72.958 71.533 69 62 ]9 58J14 11624 16 19 18 17.027 13.925 17312 .'" I 2 56 06 1}1 1 1 018 CbS t 4.4 18.815 18.781 16.13 24. 39.858 56.264 55.643 14.750 11. 11.180 1 1 4.1.653 25.680 26.656 20.392 21.582 20.539 36.33 12.291 12.MI "'" ' m) 8 9 l{ 1.25 1.67 1.95 157 IJ) I.. I.. 2.12 21JJ 2.45 254 2.82 2.9 25 0.01 0.26 0.37 0.67 0.85 0.87 0." m Dtpl

165

SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SILT SilT SilT SAND LT LT LT LT LTY LT I I I I I I WWYSILT SANOY SANDY SANOY S S S S S S CLAYEY CLAYEY CUYEY CUYEY CUY SANDY Y Y LT LT LT LT LT LT LT LT LT LT LT LT LT LT LT LT LT LT LT LT I I I I I I I I I I I I I I I I I l SI SI SANDY SANDY SANDY SANDY SANDY SILT SANDY SANDY SANDY SANDY SANOY SANOY SANOY SANDY SANDY SANDY SANDY SANDY SANDY SANDY SANDY SANO SANDY SANDY SANDY SANDY SANDY SANDY SAND S S S S S S S S S S S S S S S S S CLAY SANDY S 222 (0) . 5.222 46 272.167 978.889 931.792 1433.444 18J3.S56 1674.(0) 1 4 4 4058.889 5128.150 9456.17S 6691. 5021.661 5384.661 5742 5841.(0) 8Il2S.l11 8495.179 8J!iU56 8 1020.(0) 11)119.440 10622.222 10319.440 44 (.8 1 m 468 .911 ,2 , . 8 )1.211 78.431 S5 80 84.133 " 44.1~9 9J.2J3 60.952 I80A56 I05.1JJ 11 120.911 121.'189 101.531 113. 112.033 156.033 110.256 108.150 100.139 153.m 1 1 1 341 S27 . 1.119 1. 1.608 2.(N)) 7.050 IH·B 14.19 1515 l1.m 12.419 16.1l'l ~ 1~.SJ1 4 4 4 2 oIG 25.935 34.95 36.014 3l.936 61.841 3H39 34J1J 16.138 m.526 8 293 349 .691 ~.228 4. 4 2.791 2.871 2381 2.11 2.198 2.901 2JI0 2.m lJOO 3.261 3.122 3.141 3.160 6.122 5.079 ' 5.350 3.m 1.Q96 1 2 7 41 4 4 (m , 1.2 1.518 u. 2.66 2.845 2.993 0.1 0.250 O.lOl OJ31 3.1 6.192 OJ" 1989 "" 1,. 4156 0.155 (1.512 0.961 .{I 10.589 L66S L'" 1.051 1.945 1.471 1.695 1.765 1.262 1.)J1 L681 1.101 11m 2.1(.8 2.001 2.644 0.981 0.S31 0.888 0.821 0.976 W5 93B15 III 456 061 161 137 , , , 097 971 010 554 8.\1 , , , , , . . (11 OS 79 79 95 9S1S2 % 85 SI.811 81.m "'" 99 93.347 94 9U71 1I1.~ \JI.856 tl3.S56 WI.640 l 112 101.994 1 852.139 8 33 661 .667 . .1 .944 8 34 163.661 209.111 261.(111 OOW 668.111 665.333 959.m J79J1S 980.836 692 6 6lW3 llJJ.444 l 113 1962.222 1931.889 160s'615 1268.3)3 1 1 1 1 1 2595 6243.889 52.'9.(0) 4 .l461.(0) 1 87 8 00 1 1 19.486 25. 25.601 26.280 JH90 31.051 72.2 78.389 34.111 35.610 34.154 50.441 }1.730 44.2-10 40.818 40. 43.930 41.565 4<'" 69.216 972.5SO S07 690 1. 1. \OJ-' 21.690 2 50.2."1(1 61J.5W 62.590 OIJJJ 6-\.467 65.911 35.m 54.0J9 55.130 58.169 55.130 5(l.L'O 55.m 56.ISS 6 12.911 1ll.640 103.093 109361 990.169 11 2 USl LlO8 IJ" U!i2 1. 1J6<) 1300 1.195 1.784 1.712 1.448 1.326 1.438 1J53 "" "" 1.141 1.155 1.793 1J33 3.000 1261.558 4 8 S5 1 450 .933 . 4 4 1.1 H53 7.821 l1n 5.649 5.850 5.781 8.03 on 8.m 1. 1.'" "" 10 10.186 11.959 10.509 11.154 12.18.\ 1Hi62 1 1093.902 4 2 1 191 138 527 m 935 0 9J6 577 84 m , , , , , , . , 1.1!8 4, 4 17 11.419 13.443 16.312 15151 1 U007 41.119 44 41.341 41.608 40 26 25 2 35 34 349S1 36 61. }u]9 W,450 1 4 4 671 626 81 . . . 9.89-1 36.2SO lt196 50 56.472 5W8 81.403 so.no ~.'" 4 41.89S 47.473 46.679 46 20 22,\1 23.071 -10.958 35.330 19.372 "J" 317.490 1463351 2 JlI2 441 , 8. g,734 1 3.694 "" 18.515 18.362 17.46 '"'' 3O.~ 28.195 4 24.379 24567 36.1(11 32.160 32.829 32.975 31.244 38.549 30.628 3O.m 19.501 58 559 839 , .4 .973 . 4 1 "'~ 70.141 70.074 8lJ50 59 59.964 55.681 59.251 54 52.128 59.861 6JJ54 S3.861 59.m '"'' 10944 4J.S80 61.108 60 64.549 ".6\9 8 J81 .222 1.781 9.018 9.m 8 8 "" .'" Il964 I17Sll 12.071 14.243 14.944 13.833 13.688 18.63 19.219 15.140 10.on 10.815 21.818 21.031 WII! " 9.~ JJ! Jm lOI lW 5.(13 7.15 9.52 3.16 lJJ 5.61 6.07 758 5.75 5J! '" '" 8." ,. 1.95 '" I."

166

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173

174

LT LT LT I I I S~~DYSILT SA.~DYSILT SA~DYSILT S~~DYS SA~DYSILT SA.~DYSILT S~~DYSILT SA~DYSILT SA.~DYSILT SA.~OYSILT SA~DYSILT SA.~OYS1LT SA~DYSILT SA~DYS S,"'~DYS SAl'DYSILT SAl\DYSILT SAl\OYSILT SAl\OYSILT SAl\OYSILT SAl\OYSILT SA.~OY SA~OY SA~OY SA~DY SA~DY SA~DY SA~OY SA~DY SA~OY SA~OY SA~OY SA~OY SA~OY SA~OY SILT SILT SILT SILT SILT SILT SILT SAl\OY SILT SILT SILT SAl\OY SILT SAl\OY SILT SAl\DY SILT SAl\OY SILT SILT SAl\OY SILT SILT SAl\OY SILT SILT SILT SILT 500 OCO 0c0 0c0 .661 .833 . 1 1 l 29.833 1 44 7 j822.8JJ mlJJJ lO86.161 52211 llJ9.0c0 5692.667 1515.833 1781.661 18IS.0c0 1 46&-1J33 61 6')Je. 6891.8JJ 6161.0c0 614 61J9. 6603.833 63tUJJ 6 8Il4l.833 1 1 1 &:1 m 931 m '" , . .1 , . {I9.m 98 91 90.115 '/S SoI,1I1ll 89,100 81.411 86 8350l " \04.431 tIl.96 IOlJl llI.411 101.{195 111.84 118.311 111.111 111.%1 1I5.JJJ 1 82 MB 417 . .1 . 4-1.597 23 21 21 29.415 28.152 21542 21.993 2HJl 35.601 36.412 lUll 35560 31.1Sl 31.m 36.m ".961 14.490 16.86.\ "'" - 1 4 9\l .. . 414-1 411)9 WI WI 40.\6 J.601 4 HII J.7)j ),911 l71l4 lOll '.619 ),Oll }.l1P. '!ll 11161 1.'125 11 1086 1 ''' 'Jfl '692 \.14-1 USI J Ill> 1.812 1.081 1.116 1580 ' 4.147 2.14-1 2189 2.216 2,6S] 2113 7.491 ll99 I'" 1119 '''' ISl . 1~9 UOJ U. U. U' Li07 LlS9 IJS') IllS IJll illS '466 1.186 1.491 1.058 1151 1314 1314 2.216 2 "" 00 01 i67 m m , 7 951 . . . 2.612 &. 0 1 11.968 .~l 9-4.~1 9-4 91.-183 91.058 91.318 93 91.207 8.l.4JS om "J. IOj " 119,9157 112,1 100,698 10213l 100JJl 1 7 1 500 21.161 J11.6SO m,66 2211661 IJS1J33 Illl,6SO I Im]]l 14 1101.\100 1258.661 1111.361 1927.0c0 1182,J3) 1ll2.500 1lll.JJJ 1 2~20, 2188.161 2762JJJ 2f.U66 3374.333 1OO80c0 1159.161 m m . ~"' J3.~ U5 J1.SJ(I 39,l93 35.m 3l 310ll li "400 11110 11m 43.863 44.34J 41.OlJ 46.420 44831 45.430 -I6.1Il 37,65) 'Ull 50 130 130 1 ...... 41.985 45. 4j.JSO 21.6\10 IS.l3O 6S.1SO 60.120 35.95) 60.520 55 5J.49J 50120 5Ol20 50120 50110 SOl20 15 1tl2S " .'" . .. .. 1.~21 UI] WS IH9 1. 1.J8.1 1.4.16 1.218 1.5$4 1.835 1.551 1.456 1.490 1.399 1.389 1.140 1.J9J 1m 1m 2,0).1 , 4 JJJ . 924 .11 . J.J51 l.4l6 "" 1 Ul2 911f1 9.161 9.401 9.JJ1 OJ" 8.111 9 8.939 "61 ,-'" IO lum 12.8.l{I 11.491 10.330 10542 Jl 82 S9J .1 . H 21 24.490 28.152 21542 26.865 27.417 23.648 21.993 2 ]6.011 35.1ID 31.115 39'163 lUll 31560 31.m 29.m ".8Ol .l6.m 1l "'" 1 361 .\6IJ .. .921 . 7. 9.593 9.)9l! 1.S03 ~ ~m IS.28IJ ~1 41.\100 45 40.31 41.862 41910 4l.512 4 4 4 JJ.802 );Jm 3 '!1" .l6.ll3 .I6.m 1"" 169.400 1 1 0 1 1 259 .. .195 . 1 17.8&1 18.3 19.886 16.413 1 ~ 29.310 21831 26.JJ5 2O.1ll 26.9 21.m l8.ISS 30511 31508 lW 3lJJl 12 11.621 18.4% 15.85; 7 1.768 '~l ~.J2J IMI2 61.1-10 60.615 66.96 62.112 59.US 6lJ4S OJ. 6l1lJ 65.m 'Ol .lJ6l .JOJ 11.4J1 "." 1113J 19j1l 1 I"" 1 Il 80 206 16 OJI 610 .1 ...... I.l U9J 9,191 8358 8 ". Itll5 11 14 11.600 11132 1\.112 10.01l 10511 " Itl69 I 11 10.891 11 10.034 10.388 1 98 . .81 7.49 1J1 1 m~ ~7 4S.70 41.95 41.14 48.49 48.6 4 4 -18.28 4 ".!l "'01 "''' "''' "'" "'. "" ". .", ".

175

Appendix C

XRD Patterns

176

Zone and 1b

10 20 30 40 50 60 '2B CuKa

Zone 1e

' '''_~"_ "I. 5.31 m 5.59 m 5.60 m 5.31 m 5.89 m 5.59 6.06 m 5.60 6.84 m 5.74m.... __ ~~ ~~ 5.89 m H~~ 6.06 7.65 m 6.84 7.95 m 7.14 .'1...... ,.., ·u , 8.46 m

7.65 "V' ...... "' ''' 7.7.58595 ~~iiiiii~~~iJ~I~~ 9.5288.46~~.83 ~.;;1 10.169.87 m 10.2810.35 10.569.6 m~ ~I~~~§iiiiiili .§ ~

fO 20 30 40 50 60 '28 Cu Ka

177

Zone ld

l1.77m ......

11.90m ......

12. 12 m r::::::::::::::::::::=:....---- II ----I ~-ll -~I--~J_I----i

.43 m 12.43m ...... 10 20 30 40 50 °28 CuKa

Zone le

12.54 m 12.54 m 12.95 m ...-- r--'.. ~~ " ~ jl 12.95 m ~ J J. 13.14 m 13.14 m 1113.45 m 13.45 m --'\ .A 13.71 m 13.71 m ~ Jl ,J\. Ii 14.06 m 1 4.06m ..... 14.28 m 1 4.28 m ...... ~14 . 32 m 14 . 32 m 14.40 m 14.4Om .H 14.7 7m 14.77 m .N ·14.99 m 14.99 m LJ 'dl ,= ft Dol mite ~mit e 15.01 m 15.01 m 1 1 ~ 10 20 30 40 50 60 °28 CuKa

178

Zone 1f

17.60 m 18.19 m 19.26 m 19.45 m 20.27 m 20.72 m 20.96 m 21.59 m 21.90 m

m m

26.71 60 /0 20 30 40 50 ' 2(} Cu Ka

Zone 2

10 20 30 40 50 60 °2 (} Cu Ka

179

Appendix D

Carbon and Nitrogen Isotopic Composition of Bulk Organic Matter Data

180

Depth (m) 15N vs. N 13C N% C% C/N Air VPDB

31.58 7.24 -26.53 0.03 0.21 7.17

31.692 8.08 -22.69 0.05 0.12 2.96

31.74 7.02 -21.18 0.06 0.12 2.30

31.868 6.38 -21.71 0.05 0.13 2.71

31.948 5.92 -22.59 0.05 0.13 3.04

32.06 5.55 -22.00 0.04 0.10 2.78

32.124 5.61 -22.41 0.05 0.11 2.72

32.204 5.67 -23.21 0.04 0.09 2.33

32.204 5.60 -23.60 0.05 0.09 2.30

32.316 5.24 -20.70 0.05 0.15 3.61

32.444 5.28 -21.12 0.05 0.13 3.15

32.476 5.40 -21.44 0.05 0.12 2.99

32.604 5.13 -21.04 0.05 0.14 3.43

32.684 5.86 -20.64 0.05 0.17 4.27

32.892 6.17 -21.32 0.04 0.12 3.08

33.0306 5.19 -20.70 0.05 0.14 3.27

33.0918 5.23 -22.09 0.05 0.14 3.64

33.1428 5.29 -20.36 0.05 0.16 3.96

33.1734 5.49 -20.49 0.05 0.14 3.24

33.2142 5.34 -21.54 0.05 0.14 3.37

33.2754 5.57 -18.63 0.05 0.19 4.60

181

33.3672 5.27 -20.52 0.05 0.14 3.45

33.4488 5.21 -19.60 0.05 0.16 3.60

33.4692 5.30 -19.59 0.05 0.14 3.28

33.4896 5.31 -23.44 0.05 0.15 3.80

33.6528 5.16 -22.07 0.04 0.16 4.14

33.765 5.71 -19.14 0.05 0.24 6.18

33.7956 5.38 -23.05 0.04 0.15 3.85

33.9894 5.76 -21.37 0.04 0.16 4.50

34.0302 5.51 -24.51 0.04 0.23 6.99

34.122 5.08 -23.75 0.04 0.13 3.69

34.1832 5.10 -22.92 0.04 0.12 3.56

34.1832 5.35 -22.64 0.04 0.14 4.01

34.2648 5.18 -22.37 0.04 0.14 3.67

34.3362 5.09 -22.80 0.04 0.13 3.84

34.4484 5.27 -22.24 0.04 0.14 3.69

34.5198 5.26 -22.06 0.05 0.15 3.92

34.6116 5.43 -21.85 0.05 0.14 3.13

34.7238 5.30 -20.27 0.05 0.17 3.52

34.8462 5.47 -20.35 0.06 0.16 3.18

34.8462 5.66 -20.74 0.05 0.18 3.97

34.9176 5.54 -21.51 0.05 0.18 4.03

34.989 5.72 -20.39 0.05 0.15 3.32

35.04 6.21 -20.05 0.06 0.15 2.66

182

35.1012 6.74 -21.03 0.06 0.14 2.54

35.1522 5.72 -21.72 0.04 0.13 3.82

35.2032 5.68 -18.16 0.07 0.15 2.67

35.2746 6.64 -19.77 0.06 0.17 3.24

35.295 6.49 -21.36 0.06 0.13 2.47

35.3358 6.28 -20.96 0.06 0.12 2.23

35.3868 5.98 -20.43 0.06 0.12 2.46

35.397 6.04 -21.18 0.06 0.12 2.48

35.448 6.05 -21.64 0.05 0.13 2.79

35.5602 5.32 -21.69 0.04 0.11 3.01

35.703 5.79 -21.77 0.05 0.15 3.57

35.7642 6.21 -20.56 0.04 0.18 5.07

35.8968 5.77 -20.02 0.05 0.10 2.20

35.9376 5.82 -21.03 0.05 0.13 2.74

36.1288 5.98 -20.93 0.05 0.12 2.58

36.2576 5.58 -20.36 0.06 0.12 2.45

36.3059 5.36 -19.79 0.06 0.13 2.63

36.4347 5.73 -20.72 0.05 0.12 2.65

36.5313 5.59 -20.24 0.06 0.13 2.41

36.644 5.67 -20.33 0.06 0.13 2.51

36.7567 5.82 -20.71 0.06 0.17 3.44

36.8211 5.57 -20.84 0.05 0.16 3.65

36.9177 5.80 -20.52 0.06 0.15 2.91

183

36.9821 5.57 -19.28 0.06 0.14 2.63

37.0143 6.28 -19.38 0.06 0.17 3.26

37.0787 6.15 -19.61 0.06 0.17 3.28

37.127 6.05 -20.64 0.06 0.18 3.73

37.2075 5.97 -20.97 0.05 0.17 3.55

37.449 6.28 -20.84 0.05 0.16 3.53

37.5939 5.40 -20.99 0.05 0.16 3.90

37.6422 5.37 -19.89 0.05 0.18 3.96

37.7549 5.10 -21.17 0.05 0.18 4.57

37.8193 5.73 -20.71 0.05 0.18 4.16

37.932 5.35 -20.01 0.05 0.18 4.49

38.0286 5.55 -20.84 0.05 0.20 4.65

38.1091 5.67 -20.40 0.05 0.18 4.12

38.2057 6.27 -20.49 0.06 0.21 4.06

38.254 5.66 -17.75 0.07 0.27 4.33

38.3667 6.63 -19.72 0.06 0.21 4.18

38.4633 6.22 -20.42 0.06 0.18 3.62

38.5921 6.22 -20.04 0.06 0.17 3.06

38.6404 6.12 -21.31 0.06 0.21 4.47

38.7048 6.00 -20.93 0.06 0.18 3.50

38.7531 6.73 -20.63 0.07 0.18 3.21

38.8336 6.61 -20.26 0.06 0.18 3.32

38.9463 6.53 -20.50 0.06 0.17 3.22

184

39.2725 5.94 -20.60 0.05 0.14 2.99

39.545 6.10 -21.10 0.05 0.19 4.27

39.5995 5.93 -20.18 0.06 0.17 3.55

40.308 6.34 -19.07 0.06 0.21 4.02

41.1065 6.03 -20.47 0.05 0.18 4.01

41.18 5.93 -19.86 0.06 0.19 3.78

41.5615 5.26 -18.25 0.07 0.27 4.76

41.8885 5.62 -20.58 0.05 0.21 4.47

42.015 5.52 -20.79 0.05 0.21 4.77

42.1365 5.84 -21.68 0.05 0.18 4.24

42.2625 5.47 -20.21 0.05 0.23 5.19

42.42 5.59 -20.04 0.06 0.24 4.88

42.504 5.38 -17.93 0.06 0.30 5.69

42.5775 5.05 -17.95 0.06 0.37 7.18

42.6615 5.46 -20.53 0.05 0.24 5.49

42.7035 5.33 -20.14 0.05 0.27 6.56

42.735 5.13 -20.79 0.05 0.24 5.60

42.8715 5.46 -21.44 0.04 0.24 7.13

42.924 5.59 -19.41 0.04 0.24 6.25

42.9765 5.33 -20.66 0.05 0.25 6.23

43.1235 5.18 -19.48 0.05 0.29 6.60

43.1865 5.00 -19.12 0.06 0.34 7.05

43.218 4.70 -19.12 0.06 0.34 7.05

185

43.2915 5.10 -19.56 0.05 0.31 7.88

43.323 4.99 -19.22 0.05 0.32 7.22

43.3755 4.88 -18.35 0.05 0.32 6.99

43.5435 4.01 -20.22 0.05 0.39 9.51

43.638 4.45 -19.88 0.05 0.32 7.12

43.6695 4.41 -20.23 0.05 0.40 9.21

43.6905 4.37 -19.56 0.05 0.37 8.24

43.848 4.23 -19.89 0.05 0.39 9.28

43.9005 4.34 -20.24 0.05 0.36 8.50

43.9635 4.13 -20.32 0.05 0.35 8.46

44.0475 4.88 -20.15 0.05 0.35 8.31

44.1 4.66 -20.33 0.05 0.34 8.04

44.1315 4.95 -21.69 0.04 0.30 8.35

44.184 4.72 -20.94 0.05 0.33 7.96

44.31 4.71 -20.55 0.05 0.31 7.93

44.3415 5.39 -20.64 0.05 0.32 7.54

44.4885 5.15 -20.07 0.05 0.37 8.00

44.562 4.34 -21.21 0.04 0.33 9.04

44.625 5.02 -20.12 0.05 0.37 8.43

44.6355 5.12 -22.04 0.05 0.39 8.87

44.7405 5.24 -19.74 0.06 0.37 7.44

44.7825 5.39 -19.44 0.06 0.32 6.43

44.8035 5.16 -19.99 0.06 0.34 7.17

186

44.835 4.68 -20.07 0.05 0.35 8.23

44.8665 4.37 -21.72 0.04 0.35 9.40

45.054 5.49 -23.32 0.07 0.68 11.34

45.0762 4.28 -20.23 0.05 0.37 9.20

45.1143 4.53 -20.80 0.05 0.43 10.06

45.2667 4.16 -21.50 0.05 0.47 11.28

45.2921 3.71 -21.95 0.05 0.55 12.07

45.4318 4.52 -22.27 0.06 0.52 10.58

45.4445 4.26 -21.91 0.05 0.50 10.67

45.4572 4.05 -23.61 0.03 0.32 13.56

45.4953 4.82 -20.46 0.06 0.49 8.99

45.5715 4.11 -21.69 0.04 0.41 11.85

45.7493 5.01 -20.04 0.05 0.44 9.67

45.7747 3.51 -22.39 0.05 0.59 13.67

45.889 3.82 -21.80 0.05 0.49 10.55

45.9525 4.79 -20.64 0.06 0.52 9.71

46.0287 4.01 -21.20 0.06 0.57 11.42

46.0668 4.93 -19.95 0.07 0.51 8.69

46.1684 4.53 -20.91 0.06 0.51 10.46

46.2573 4.29 -21.00 0.06 0.55 10.40

46.3462 4.14 -20.55 0.07 0.59 10.12

46.5113 4.25 -21.58 0.06 0.58 11.78

46.6256 4.02 -21.57 0.06 0.60 12.08

187

46.7018 5.44 -21.28 0.09 1.17 15.11

46.8161 5.77 -22.87 0.05 0.42 9.12

46.8669 5.57 -21.83 0.06 0.58 10.61

46.9304 4.89 -22.21 0.06 0.55 10.88

46.9939 4.93 -22.08 0.06 0.56 11.72

47.0828 4.76 -22.50 0.05 0.43 9.23

47.159 5.45 -22.48 0.06 0.56 11.29

47.2352 4.39 -21.91 0.06 0.53 10.47

47.3114 5.03 -22.24 0.06 0.61 12.14

47.3749 4.50 -23.43 0.05 0.51 12.96

47.4892 4.97 -21.44 0.06 0.46 8.65

47.6161 5.21 -22.32 0.05 0.45 9.92

47.6924 5.35 -21.03 0.06 0.55 10.26

47.7686 4.90 -20.34 0.07 0.52 9.01

47.8067 5.98 -23.18 0.09 1.08 14.49

47.9083 6.23 -23.30 0.08 0.70 10.30

47.9845 6.17 -26.28 0.08 0.93 13.36

48.0384 8.05 -24.73 0.10 1.31 15.21

48.1408 6.54 -25.20 0.10 1.50 16.79

48.2176 7.91 -24.22 0.11 1.42 15.05

48.2816 8.18 -23.59 0.05 0.43 10.67

48.3328 7.12 -24.46 0.05 0.58 12.33

48.3584 8.49 -23.93 0.04 0.61 16.71

188

48.4096 7.12 -23.65 0.04 0.43 11.77

48.4352 8.16 -23.73 0.04 0.41 11.07

48.4864 7.16 -24.08 0.06 0.62 12.68

48.5504 6.59 -23.98 0.04 0.41 12.58

48.6061 6.97 -24.14 0.05 0.50 12.64

48.6061 8.76 -23.74 0.05 0.37 9.27

48.7168 7.97 -23.68 0.05 0.46 10.81

48.768 6.65 -24.26 0.07 0.70 11.06

48.8192 7.90 -24.31 0.08 171 23.63

48.8704 7.75 -24.24 0.07 0.81 12.96

48.9088 8.64 -25.54 0.18 4.36 27.71

48.9984 7.40 -23.36 0.05 0.40 8.76

49.0496 7.70 -22.76 0.05 0.36 7.78

49.1648 8.17 -23.52 0.07 0.74 13.00

49.28 7.36 -22.58 0.05 0.31 7.05

49.3568 7.90 -22.91 0.05 0.36 8.94

49.4967 7.75 -23.24 0.05 0.43 9.88

49.53 8.37 -22.16 0.05 0.25 6.40

49.6384 9.47 -23.48 0.05 0.39 9.37

49.8176 7.73 -23.04 0.05 0.17 4.33

49.92 8.63 -24.61 0.05 0.62 14.23

49.9712 8.85 -24.42 0.04 0.43 11.88

50.0608 8.44 -24.13 0.05 0.51 12.11

189

50.1112 8.64 -22.71 0.03 0.27 9.57

50.1632 8,25 -22.60 0.02 0.15 7.03

50.24 8.76 -23.69 0.04 0.47 12.35

50.3552 7.76 -23.27 0.03 0.22 8.50

190

Appendix E

Carbon and Oxygen Isotopic Composition of Calcium Carbonate Data

191

13 18 Depth (m) δ Ccarb(‰) δ Ocarb (‰)

0.0117 -3.34 0.29

0.2574 -3.02 0.46

0.2691 -2.64 0.57

0.3744 -2.67 0.71

0.5031 -2.77 0.67

0.6669 -3.45 0.29

0.8541 -4.57 0.53

0.8658 -5.15 0.53

1.0646 -4.78 0.51

1.2519 -4.21 1.43

1.3689 -4.23 1.08

1.5678 -4.96 0.60

1.6731 -3.61 1.17

1.8603 -3.73 1.37

1.9539 -3.51 1.13

2.1177 -3.34 0.93

2.1996 -3.48 1.84

2.4453 -3.69 1.78

2.5389 -3.21 1.29

2.5858 -3.28 1.43

2.7864 -3.23 1.32

192

2.8197 -3.37 1.63

2.9835 -3.52 2.18

3.0109 -3.47 0.84

3.0872 -3.68 2.45

3.1635 -3.65 3.02

3.3707 -3.22 5.64

3.3815 -3.14 5.70

3.6867 -2.47 5.85

3.7521 -2.34 6.03

3.8393 -2.47 5.95

4.0464 -2.66 5.60

4.09 -2.96 5.16

4.2 -3.02 4.99

4.3952 -3.46 4.70

4.51 -4.25 5.28

4.669 -3.51 5.26

4.812 -4.78 5.21

5.033 -4.09 5.21

5.319 -4.91 3.96

5.592 -5.01 4.87

5.605 -4.95 3.99

5.748 -5.13 4.12

5.891 -5.18 3.81

193

6.0674 -5.13 3.82

6.4381 -3.69 4.06

6.8425 -5.46 3.58

7.1458 -5.58 3.33

7.5839 -5.54 3.50

7.6513 -5.60 3.72

8.4601 -6.24 3.51

8.8308 -5.27 3.69

9.52 -4.17 3.33

9.69 -4.03 2.74

9.87 -4.39 5.11

10.04 -4.47 3.95

10.16 -4.58 4.61

10.28 -3.51 4.08

10.56 -3.71 4.08

10.93 -3.66 4.01

11.0486 -3.32 4.06

11.2574 -3.68 4.72

11.5184 -4.13 4.89

11.6576 -0.35 4.06

11.675 -3.88 -4.86

11.7794 -4.79 -2.92

11.9012 -3.66 -2.71

194

11.9882 -3.42 -2.61

12.01 -3.33 -2.44

12.12 -2.95 -1.48

12.43 -3.41 -2.68

12.54 -2.34 4.25

12.77 -3.20 3.70

12.95 -3.35 1.32

13.14 -3.62 3.43

13.45 -3.58 4.75

13.71 -3.61 4.68

13.83 -3.63 4.70

13.94 -3.73 4.71

14.06 -3.78 4.77

14.09 -3.81 4.75

14.17 -3.88 4.73

14.21 -3.84 4.70

14.28 -3.98 4.76

14.32 -3.97 4.71

14.4 -4.07 4.86

14.77 -4.30 5.14

14.89 -4.38 -1.75

15.01 -2.11 4.28

15.17 -1.80 3.80

195

15.22 -1.66 3.89

15.36 -2.12 3.45

15.66 -1.14 3.84

15.71 -1.02 3.69

15.85 -1.09 3.67

15.94 -1.10 3.74

16.3388 -2.20 3.47

16.9856 -1.10 3.59

17.1088 -2.65 2.99

17.3552 -2.05 3.42

17.6016 -1.79 3.39

17.9404 -1.66 2.35

18.164 -2.84 2.83

18.6888 -3.41 3.03

18.8528 -2.97 3.64

19.00168 -3.07 3.30

19.1644 -3.04 2.85

19.2628 -2.86 2.84

19.312 -2.75 3.03

19.7712 -2.86 3.48

20.2632 -2.80 2.69

20.6076 -3.17 3.39

20.7224 -4.75 3.57

196

20.9 -3.88 2.76

20.9684 -3.68 3.58

21.018 -3.64 3.36

21.072 -3.70 3.28

21.09 -3.69 3.29

21.126 -3.72 3.37

21.162 -3.78 3.30

21.234 -3.44 2.77

21.288 -3.06 3.04

21.36 -3.74 2.85

21.504 -3.88 2.68

21.648 -4.17 2.58

21.81 -4.21 2.77

21.9 -4.22 2.81

23.104 -4.77 3.09

23.3328 -5.04 3.63

23.4576 -4.53 3.49

23.8112 -4.30 3.17

23.936 -4.47 3.05

24.01 -4.32 2.99

24.8294 -3.96 2.89

25.2298 -4.25 2.65

25.2298 -4.53 2.58

197

26.717 -4.82 2.82

28.2 -4.20 2.60

30.577 -3.81 2.53

31.516 -3.43 2.40

31.58 -3.30 2.36

198

Appendix F

Major and Trace Elements Geochemical Data

199

m 0 0 JI J6 JJ JI JJ 62 75 75 94 95 70 70 67 68 65 57 58 66 60 7 89 Z, 11 105 " I 7 V J4 79 79 96 9J 82 85 86 86 89 86 80 8' 8 101 108 109 109 126 169 196 102 219 2IJ "m 05 04 06 05 05 .04 . . . . Tf % 0.05 0.06 0.07 0.04 0.05 0.04 0.05 0.05 0.05 0.06 0.08 0.06 0.07 0.07 0.04 0.05 0.05 0.05 004 0 0 0 0 0 7 8 81 86 8 40 S. 193 1 Ji2 752 441 431 439 285 280 283 2 2 631 350 380 364 686 645 685 697 699 600 50 3 7 7 7 5 5 5 8 9 9 9 9 6 6 6 12 12 17 10 10 10 10 II II II Pb 0 0 0 0 1 1 1 20 00 P 0 930 750 900 920 606 670 640 128<1. 11 106

200

7 0 Il 75 75 76 78 7 41 91 76 63 94 6J 38 36 55 69 56 50 58 56 85 80 89 86 86 8 71 12 96 97 98 91 97 96 72 52 8J 81 85 80 16<1 173 101 171 111 146 106 102 102 109 110 200 4 03 . 0.01 O.oJ O.oJ 0.05 0.05 0.05 0.05 0.05 0.06 0.04 0.04 0.03 0.03 0.03 0.03 0.02 0.02 0.04 0.05 0.05 0.06 0.05 0.03 004 006 0 176 169 412 429 211 297 236 250 298 286 244 234 263 287 319 329 302 3J1 339 324 304 316 534 5J7 10000 10000 > > 7 7 7 7 9 3 9 9 9 9 6 6 6 6 5 5 8 8 8 8 8 4 4 11 " 0 0 9 20 30 80 40 290 230 7 520 220 77 89<1 680 810 159<1 1l9<1 1l9<1 12 144 14 14 1250 1080 1810 1690 1070 1600 1460 1980 1120 !370 1 1 1 1 8 42 42 41 47 44 J9 25 26 51 77 33 62 64 63 38 38 64 56 54 66 55 58 50 50 43 1 1 1 4 4 2 2 2 2 7 3 3 3 3 3 3 3 3 3 3 6 5 5 10 16 22 ' 141 548 548 546 566 423 409 445 419 446 407 4J7 260 38J 634 399 315 387 379 333 646 646 563 550 596 172 6 18 18 17 19 19 J1 21 21 21 28 29 20 20 J7 J2 24 30 38 35 33 33 30 l5 18 13 7 10 21 26 77 70 35 36 59 57 57 50 54 50 83 85 5 40 48 42 41 61 6J 68 69 62 112 2 7 6 8 8 9 9 9 11 14 13 14 14 12 15 14 14 12 12 19 10 10 Il Il Il 1 2 9 2 0.5 1.5 1.5 1.5 1.5 1.5 1.8 1.8 1.6 1.6 1.6 1.4 1.2 1.9 1.8 1.4 1.2 1.4 11 11 3.2 0.8 0.9 < 0 0 0 00 70 40 20 30 50 16<1 12 120 180 100 77 46<1 25 4 4 230 220 250 310 620 670 350 650 610 550 570 540 06 .05 .05 .04 .02 .05 .04 .oJ .oJ . O.oJ OOJ O.oJ O.oJ O.oJ O.oJ 0.05 0.05 0.05 0.02 0.05 0.05 004 0 006 004 0 006 0 0 0 O O 0 7 0 1.6 1.9 25 1.81 1.71 1.82 1.93 1.74 2,91 2.71 2.6 2.94 2.73 2.02 l78 3.02 3.05 3.06 2.95 2.77 2.69 2.26 264 0.41 0.01 0.84 0,96 7 19 .25 . 1.1! 1.05 0.21 0.21 0.1 0.21 0.23 0.28 0.24 0.27 0.24 0.29 0.32 0.29 0.26 0.25 0.26 0.25 0.26 0.26 0.27 0.19 0.32 0.29 0 0 7 2 14 . 1.6 2.l 1.51 1.31 1.63 1.53 1.53 1.03 1.6 1.46 1.42 1.43 1.27 1.54 1.15 1.14 1.04 1.14 2.06 2.13 2.02 2.28 2.04 2 0.2 0.88 7 7 4 25 77 7 . 4.1 1.13 5.72 4.88 4.84 9.11 3.5 9.89 6.01 5. 6.15 6.59 6.22 6.34 5.03 5.55 5,46 5.93 5.9 8.81 8. 8.22 8.77 8,45 10.65 7 7 7 14 U9 JJ3 1.33 1.33 1.4 1.85 1.04 1.42 1.2 1.39 1.39 1.84 1.16 1.04 1.36 1.29 1.29 !.is 0.22 0.95 0.54 0.66 083 1 1 2 7 6 6 8 .4 . . . . . 7 9 .7 .23 12 17 53 8.4 88 9.1 9.4 9. 95 98 14,1 14 14 18 14 10 12 1.84 7 5.74 4 6.77 6.6 7 3 9 9 8 1 65 .7 2 3 .4 .8 . . .7 .7 2 3.5 1.62 1.87 13.5 1.05 1.95 13.6 1.75 1.16 1.72 1.59 1.06 2.74 3.18 3.03 2.31 2.82 2.52 2.74 2.62 2,37 2 2 2 2 0 0 4 8 25 4 4 69 . .7 4.2 9546 4.51 9.52 9.87 9 10.16 10.28 10.35 10.56 5.891 5.033 5.319 5.592 5.605 5 4.669 4.812 7.1458 7.5839 7.6513 7. 6.8 8,4601 8,8308 4.3952 6.067

201

2 7 7 7 5 2 00 0 69 68 98 66 94 98 95 90 95 97 81 85 88 86 11 11 106 122 128 10 10 10 1 1 4 8 70 79 70 7 41 67 94 94 67 96 62 96 60 60 55 58 7 88 " 111 102 135 118 118 108 120 116 11) 03 04 04 05 04 02 , . . . . O.oJ 0.03 0.04 0.02 0.05 0.04 0.03 0.04 0.04 0.02 0.02 0.03 0.02 0.02 0.02 0.05 0.03 0.03 0.04 004 0 0 0 0 0 7 7 7 2 0 0 0 9 19 31 7 02 17 15 188 112 16 158 1)8 268 291 26 271 23 252 27 258 258 238 208 221 208 248 2 2 2 2 319 7 7 7 7 7 7 7 7 9 9 6 6 6 6 8 8 8 11 10 10 10 10 10 10 14 12 0 0 0 0 0 0 0 0 0 0 0 0 0 1 5 80 00 17 130 23 2 02 63 900 7 3 860 136<1 127 197 193 125 107 1340 1390 1490 1060 1950 1 1 1 1 21 225 203 2100 2 2 2 2 2 1190 6 2 71 71 70 74 79 61 70 39 35 69 65 67 9) 81 8 " 42 42 40 40 40 41 42 46 40 62 8 0 1 7 7 7 5 4 9 9 9 6 11 11 18 16 13 12 1 26 2 51 53 54 16 11 13 13 7 7 71 166 )84 )42 J25 205 )90 ))6 74 382 384 399 800 8 404 447 44 409 418 475 288 994 623 19) 1075 1125 1120 7 19 19 19 44 44 46 40 46 21 28 23 25 21 J7 20 20 29 )9 )5 )6 31 61 31 73 3 11 7 06 77 46 46 47 42 48 4 27 29 )7 64 64 35 35 96 62 66 69 69 68 69 67 68 66 83 1 8 9 9 9 13 13 13 11 15 15 14 16 18 12 17 14 14 10 14 14 14 16 17 14 14 17 1 2 .9 .7 .9 .7 1 3 4 3 0.5 0.5 1.1 1.1 1.1 1.1 1. 1.6 1.6 1.7 14 14 2.5 2.2 3A 4.8 2.4 09 0 0 0 0 < < 0 20 40 9<1 180 110 190 130 130 150 280 280 250 210 200 260 250 )40 )80 )10 ))0 500 550 3 3 400 450 430 47 2 2 2 2 3 3 3 3 5 5 0 04 04 02 0 0 0 0 0 0 0 0 .03 .0 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.03 0.04 0.04 0.05 0.04 0.04 0.03 0.04 0.02 0.02 0.04 0 004 0 0 1 1 7 7 7 2 9 1 1 12 1 77 8 4 .7 . 2.7 1.83 1.63 1.4 1.85 1.5 1.86 1.98 1.56 1.29 1.38 2. 2.74 2. 2.0 J44 3.9 3.22 3.31 3.7 3. 3.54 3 3 2.5 7 2 3 6 5 J .2 25 27 2 2 .21 .21 .21 .2 .23 .23 .2 .32 .35 .25 .22 .25 .24 .22 .19 .16 .28 . . . . 0 O OJI 0.2 0.17 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 7 0 7 0 21 09 . 1.l )1 1.81 1.8 1.42 1.7 1.23 1.9 1.58 1.94 1.69 1.29 1.36 1.06 1.78 1.78 2.85 2.25 219 2 1 0.85 0.92 0.94 1 2 2 7 9 6 5 1 1 1 , 1 1 61 .3 .62 .7 . 10 10.1 1.42 1.42 1.5 1.6 2.0 2.11 7.7 3.68 7 7 5.24 8. 8. 5J8 5J6 5 8.09 106 4 9.32 9.58 6.9 1 2 2 9 9 - .2 .84 1.8 14 08 1.23 1.15 1.85 1.45 1.45 1.65 1.62 1.0 1.5 1.7 1.79 1.24 1.76 1.46 1.94 1.31 1.24 1.77 1.54 2.24 2 0.89 0.7 0.65 0.54 0.68 0 9 8 .1 .5 .6 . . 8 1.7 2 11 13 1 7.7 7.2 8A 16.4 IU 1.21 12 15 17 13.5 17.5 10.2 13.2 14.6 12,6 11.4 14.8 13.9 17.6 1 1 1 124 1 7 7 7 7 5 9 6 7 7 .7 4 67 67 0 9 9 1 .92 .73 2.9 2 1. 1. 1. 1.7 1.3 1.93 1.69 1.13 1.35 2. 2. 2. 2.05 2.56 2 J09 2 3. 3. 3.82 3.18 3.28 105 4 6 5 1 8 1 2 7 19 .43 2 14.4 11 1 12.01 14, 15.01 10.93 11.12 12.95 13.45 14.32 14.77 15.17 15.22 12.54 13.14 14.06 14.89 15.36 11.6 11.7 11.0486 11.3618 11.657 11.9012 11.9881

202

9 7 78 12 98 93 64 87 8 111 115 112 11 117 101 111 101 105 105 108 113 108 112 104 112 106 120 119 61 73 75 76 70 77 70 79 78 62 64 69 63 68 55 57 81 83 83 83 12 " 48 45 101 113 0.05 0.04 0.04 0.04 0.05 0.05 0.04 0.04 0.04 0.03 0.03 0.03 0.03 0.04 0.05 0.03 0.03 0.03 0.04 0.04 0.02 0.05 0.04 0.03 0.02 0.04 7 4 12 151 18 167 183 154 162 184 110 159 169 11 147 118 184 170 159 176 149 186 196 211 2 2ll 3420 2410 62110 7 7 7 7 7 7 7 7 7 9 9 3 3 6 6 6 6 5 8 8 8 11 11 13 14 14 50 70 40 4 4 770 17 1970 1970 1970 1 1490 21160 23110 23110 3150 2090 2590 2390 2860 2900 2640 2640 2960 2130 2610 2140 2880 2280 2950 2 71 76 61 76 68 64 67 63 65 92 58 55 52 88 85 80 85 87 89 83 " " " 41 40 102 2 7 3 5 5 8 9 6 3 11 11 11 11 12 10 10 14 15 19 21 29 22 27 21 21 J 7 7 9 178 140 m 222 717 341 393 799 64 527 503 553 520 519 431 408 44 445 455 463 482 269 211 945 1085 1335 0 41 41 40 41 24 27 29 29 27 4 29 23 26 31 36 38 34 37 51 30 33 39 38 50 11 19 71 74 76 70 7J 44 43 61 64 67 65 65 69 93 90 97 99 60 57 52 87 84 102 101 103 128 15 16 15 15 15 13 15 11 13 15 17 17 14 16 17 16 12 17 14 16 17 16 14 19 16 14 .5 .5 6 . 1 1 2 1.1 1.8 1.4 12 12 1.6 12 2.3 J.7 2.5 2 32 0.7 0.8 0.5 08 06 09 09 <0 <0.5 <0 <0.5 70 190 190 190 190 110 110 220 240 220 220 280 260 240 240 220 250 250 240 220 280 320 380 310 550 510 0.Q3 0.05 0.04 0.04 0.04 0.05 0.05 0.04 0.04 0.04 0.03 0.03 0.03 0.04 0.05 0.03 0.03 0.03 0.04 0.04 0.04 0.02 0.05 0.04 0.03 0.02 77 1.9 1.6 34 38 1.28 3.73 3.52 3.55 3.39 2. 3.63 3.53 3.01 3.37 3.08 3.63 3.36 3.34 3.55 2.64 2.51 2.96 4.68 3J8 48 .25 OJ 0.26 0.23 0.24 0.26 0.26 0.29 0.26 0.36 0.37 0.27 0.53 2.37 0. 0.33 0.25 2.72 0.24 0.24 OJ3 0.27 0.28 0.32 0.25 0.34 0.32 0 OJI 3 6 44 .18 .97 .48 1. 1.5 1.5 1.9 1.81 1.87 1.58 1.54 1.75 1.77 1.87 1.77 1.79 2.54 2.55 2.11 2.71 2.32 2.61 204 2.3 2 2 2 2 7 .5 4.6 4 5.8 1.96 1.95 1.99 5.07 5.92 7.19 7.86 7.77 7.68 4.99 4.1 4.11 4.92 4.75 4.51 4.65 4.88 2.94 2.34 6.58 6.37 308 364 9 16 46 .4 2.1 1. 1. 1.61 1.11 1.03 1.87 1.62 1.58 1.53 1.86 1.43 1.57 1.33 1.57 1.94 1.92 1.86 1.12 1.65 1.79 1.74 1.95 1 0.88 0.88 0.93 1 1 .2 .7 7 9 7.4 0.8 6.8 6.8 9.9 8.2 14 1.61 12 10. 10.6 11.9 1.39 13.6 7.0 7.56 3.24 3.53 4.83 7.12 5.69 6.61 0.88 5.67 6 17 .4 . .84 JJ 24 32 1.78 1.77 1.89 1.99 3.14 3.17 3.21 3.77 3.16 3.57 3.62 3.65 3.89 2.99 2.98 2.47 2 2 364 328 3.25 2.87 2 168 756 1088 1968 2632 9856 7712 6888 8528 6076 6732 .4 ...... 15.48 15.71 15.85 15.66 15.94 19.64 18.164 16 17 18 18 18 18 19 16.3388 17.0164 17.9712 17.6016 19.2628 19.4596 20 20 20 20.1156 20.2796 19.00

203

1 0 0 5 4 05 79 47 4J J9 J9 4 76 76 79 76 8J 63 67 64 60 52 59 50 59 6 84 89 8 8 1 1 1 7 7 5 J2 J5 J4 J4 J8 J4 24 26 71 37 56 82 5 5 12 42 4J 96 69 64 64 60 63 63 6 10 1 1 2 2 3 3 2 2 2 1 1 01 01 01 07 07 03 01 0 0 0 0 0 0 0 0 0 0 .0 . . 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.01 0.03 0.04 0.03 0.03 0.02 0.03 0.03 0 0 0 0 4 6 13 04 74 70 65 68 53 50 48 III l7l 122 109 158 136 108 115 150 144 133 150 147 147 III 1 29 2 7 7 3 3 3 8 3 5 5 5 5 5 5 8 8 8 4 9 6 9 6 6 6 6 6 6 , 0 70 0 440 440 790 750 980 620 620 640 8110 850 820 11110 172 1030 1590 1550 1510 1040 1880 1160 1540 1 2120 2000 2110 2 2 ll110 7 7 6 18 1 29 J9 J4 2J 26 26 73 70 II II 37 35 62 60 61 58 56 52 55 52 6 12 40 0 1 1 1 1 2 2 2 7 7 7 3 3 3 3 2 6 5 5 5 8 8 4 , 1

204

2 7 8 72 76 7J 7 91 51 97 94 94 61 77 90 63 60 66 83 82 85 83 6 89 89 80 5 7 5 0 33 00 71 71 71 71 61 69 33 38 63 60 62 69 9) 6) 81 81 80 6 85 8 46 4 119 110 105 174 1 2 01 .D3 .D3 .D3 .D3 .D3 . 0.D3 0.D3 OOJ 0.D3 0.D3 0.D3 0.D3 0.D3 0.02 0.02 0.02 0.04 0.02 0.04 0.03 0.04 0.02 0.03 0.03 0.02 0 0 0 0 0 0 4 2 0 0 3 3 3 04 71 8 43 48 48 49 43 46 46 45 41 42 4) 4 99 58 54 6 5 5 17 115 149 1 20) 7 7 7 7 7 7 9 9 9 9 9 9 9 9 6 6 6 10 10 10 15 11 13 15 13 " " 0 0 2 )0 00(1() 840 150 160 180 140 150 140 230 200 2)0 340 340 310 370 500 ])0 420 900 960 990 6 16 177 1840 9 5500 " 3 2 0 6 6 27 22 25 2J 24 24 2) 2) ) ) )) 2 2 31 31 31 31 62 32 35 33 34 50 44 4J 5 I I I I I I I I I 2 2 9 3 6 6 5 8 4 II 1 30 " " " " 8 3 10 7 7 2 3 7 82 82 82 88 8 8 101 11 118 127 115 110 109 166 166 119 159 136 203 722 535 151 445 16 1805 6 5 15 19 40 21 27 22 23 25 20 24 25 26 22 26 )1 )5 2 28 28 28 28 )0 2 31 35 37 0 7 0 5 47 46 27 20 68 61 61 51 69 62 51 66 53 52 55 56 55 56 58 57 52 6 5 44 9 4 9 9 5 9 9 8 8 15 15 11 17 16 11 16 10 10 10 10 14 II II II II II II " 5 5 5 .5 .5 .5 . . 8 0.5 0.5 0.5 OJ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0 0 II II 1 2.5 0.5 OJ 06 <0 <0 <0. <0 < < < < < < < < < < < < "'.5 "'.5 < 30 30 30 30 60 60 60 50 50 50 50 50 50 50 50 50 80 40 40 40 40 100 160 130 230 240 04 OJ .D3 .D3 .D3 .D3 .D3 .D3 .02 .02 .04 .03 .02 .04 .02 .03 . 0.D3 0.D3 0.D3 0.D3 0.D3 0.D3 0.01 0.02 0.03 0.02 0 0 0 0 0 0 0 0 0 0 0 0 0 O 7 0 7 0 7 6 5 8 8 1 17 1 04 92 94 9 .73 .22 .75 .7 . . . 32 36 4. 38 1.7 1.16 2 2 2 3.13 3.1 3.86 3.6 3. 3.86 3. 3.55 3.52 3.4 3 3 5 4. 4.45 4.52 4 1 7 7 6 27 .3 .2 .26 .44 OJ OJ OA 0. 0.42 0.3 0.29 0.26 0.24 0.33 0.33 0.37 0.34 0.34 0.26 0.54 0.43 0.53 0.46 0.4 0.45 0.39 0 0 0 1 2 7 0 7 5 5 8 8 4 16 2 7 7 0 9 9 .1 .4 .7 .99 . 4 28 5A 4. 4.02 4.64 4.59 4 2.3 2. 3. 3. 3. 3. 3.49 3.16 3.82 3.12 3.72 3.29 3.34 5.32 5.29 6 6 5 4 7 3 3 6 5 5 8 4 8 17 77 .7 09 .73 .93 .7 .78 .85 .7 .82 .69 .68 . . 8 0.8 0. 2.4 2.26 0.77 3. 0.77 0.7 0.7 0.7 0.7 0.7 6.82 0 0 0 0 0 0 0 4 0.7 0 0 1 0 1 ) 7 5 S 3 7 77 72 72 7 7 7 8 . 65 O I .7 . . . 0.8 0.8 0 L 1.42 0.41 0. 0. 0. 0.8 0. 0. 0.54 0.99 0.85 0.76 0.87 0.84 0.83 0.64 081 0 0 0 0 7 7 7 3 6 4 4 1 1 1 19 15 12 1 21 2 2 07 06 08 . . . .4 ...... 5.5 . 01 0 0 0 11. 1.35 1.27 1 2 3. 5 2.4 0.D7 0.1 0.12 0.07 0.08 0.13 0 0 0 0 0 0 1 0 2 3 5 2 9 6 1 23 2 98 93 97 99 9 6 88 4 .01 .18 .52 . 1. 1. 1. 1. 1. 1. 1. 1.7 1.88 1.77 1.86 1.69 1.56 1.56 1.76 1.62 1 2. 2.39 2.38 2 2 2 2 0. 3.15 2 2 6 2 2 6 8 7 28 94 54 9 84 7 65 9 14 956 7 6 8 4 12 10 7 .7 . . 44 4 2 . 28.2 1.891 31.58 31.74 32.06 32 33 34 30.577 31.516 31.6 32.316 32.4 3 33.0306 33.1 33. 33.2 33. 33.4896 33. 33.9 34.2648 34 34.5198 34.7238 34.91

205

1 7 00 74 99 94 90 96 95 98 99 95 94 94 90 9J 9J 84 84 83 89 11 101 104 10 104 102 1 7 68 75 79 79 94 98 79 72 75 70 70 70 77 65 67 66 68 7J 69 65 89 86 89 80 8 114 114 .oJ 0.03 0.03 O.oJ 0.03 0.03 O.oJ 0.04 0.04 0.03 0.03 0.03 0.03 0.03 O.oJ 0.03 0.02 0.03 0.02 0.03 0.03 0.03 0.02 0.02 0.02 004 O 4 9 2 70 53 50 59 56 58 5J 45 48 48 48 49 49 48 52 98 62 51 51 54 55 81 " 11 118 3 7 7 7 9 9 9 9 9 9 9 9 9 9 6 8 8 8 8 8 8 11 10 12 11 11 0 0 8 7 00 30 190 180 220 71 780 320 7 860 830 880 860 810 450 910 950 610 690 9 1000 1130 1490 1540 10000 3870 3450 55 4 > 7 JO J6 J6 J6 J4 J5 J5 J6 J6 J5 J6 J7 J7 J7 J7 J7 JJ 34 51 37 3 l4 11 11 42 40 I I I I I I I I I I I I I I I I I I J 2 2 2 14

206

78 72 75 74 57 7l 7l 9<) 82 61 95 99 96 90 68 69 55 66 9l 87 84 80 89 87 89 80 66 49 61 61 61 76 72 67 68 67 68 76 7] 62 69 6l 66 69 6l 6l 60 58 6l 54 88 10 127 158 1 .01 om 0.D2 0.D2 0.D2 0.D2 0.D2 0.D2 0.D2 0.D2 0.01 0.D2 0.D2 0.01 0.01 0.01 0.02 0.02 0.02 0.02 0.01 om om om om om 0 om 61 61 54 54 51 58 56 57 59 56 57 56 59 53 55 55 59 55 5] 48 60 60 65 64 62 60 62 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 8 9 9 9 9 9 6 12 10 10 " 0 2 160 130 720 710 440 410 490 440 4 280 260 200 ]0<) 60<) llO 920 600 690 ]00 580 550 520 580 850 840 830 1050 40 4l 27 28 27 22 28 28 27 27 26 29 29 29 31 ]5 ]5 ]5 ]] ]] ]0 l8 l4 l4 l4 16 II I I I I I I I I I I 1 1 1 1 1 1 1 1 1 1 1 1 2 2 10 15 15 < < < < < < < < < < 9<) 9<) 71 74 78 61 74 74 98 99 64 60 58 81 88 89 82 7l " 90 "1 141 107 104 136 162 102 1 19 18 21 21 JO 20 24 20 20 24 24 22 27 28 25 26 24 26 25 28 31 ] ]2 17 II II 26 51 55 55 58 56 51 56 56 57 5] 47 41 45 41 41 41 45 48 42 46 42 44 46 42 61 6] 17 9 8 8 9 9 12 14 12 12 14 15 16 10 10 10 10 10 " Il Il Il " " " " Il 20 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 < < < < < < < < < < < < < < < < < < < < < < < < < < < 0 40 40 40 40 40 40 4 50 50 50 50 50 50 50 50 90 60 60 60 60 60 60 60 60 ]0 60 50 2 02 03 01 01 02 . . . . . O.O} 0.02 0.03 0.02 0.02 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.02 0.03 0.01 0.01 0.02 0.02 0.01 0.01 0.01 0.0 0 0 0 0 0 92 4 .02 . 4J ]5 1.91 1.74 4.07 4.98 4 2.92 2.73 2.45 2.52 2.11 lOS 3.01 3.54 3.88 3.46 3.28 3.59 3.84 6.76 ]09 5.42 5.26 6 8.11 J 1 1 3 A 4 .44 .53 OJ O 0.51 0. 0.3 OJ3 0.23 OJ OJ2 0.49 0.46 0.43 0.46 0.42 0.42 0.38 0.45 0.5 OJ3 0.25 0.55 0.55 0.47 0.47 0.52 0 0 1 7 7 7 2 7 6 .62 .97 . 4J 4.17 4.32 4. 4.82 4.31 4.98 4.54 4.33 4.82 4.34 4 4 3.69 3.09 3.92 3.39 5. 5.12 5.63 5.68 5.83 5.75 5.28 5.0 5.13 5 9 5 4 .7 .8 .7 0.8 07 0,81 0.81 0.81 0.76 0.87 0.73 0.72 0,73 0.84 0.72 0.69 0.74 0.69 0.72 0.76 0.78 0 0 0 4 7 66 . 0.6 0.6 1.01 0.73 0.7 0.73 0.6 0.82 0.63 0.73 0.65 0.65 0.65 0.68 0.69 0.77 0 0.63 0.78 0.57 1 4 22 25 2 . . OJ 0.1 0. 0.24 0.16 0.86 0.27 0.24 0.15 0.77 0.15 0.77 0.27 0.68 0.16 0.22 0.74 0.26 0.79 0.24 0.78 0.15 0.78 0.16 0.97 0.13 0.15 0.26 0.52 0.23 0.65 0.23 0.62 0.09 0.76 0.13 0.15 0.15 0 0 73 59 82 86 09 03 IA 1.8 1. 1. 1. 1. 1.78 1.71 1.93 1.98 1.83 1.78 1.87 1.62 1.85 1.97 1.63 2. 2. 2.29 2.44 2.46 2.16 2.34 2.12 2.02 2.16 18 105 1315 . 2725 8885 . . . 41. 40.308 42.015 42 42.504 42.798 42.924 43.218 43.302 43.386 43.638 43.743 }9 41.1065 41.5615 41 42.2625 42.3465 42.5775 42.6615 42.7035 43.1235 43.1865 43.3545 43.9005 44.0475 44

207

1 6 75 70 72 75 7 43 4 61 61 63 66 66 63 60 58 53 53 59 57 162 123 106 45 42 43 42 49 40 44 40 28 26 31 33 32 35 32 36 33 37 64 52 50 50 1 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.03 0.0 0.04 om om om om om 002 002 002 002 002 7 75 70 63 57 56 56 129 124 141 161 12 120 132 140 128 166 140 168 155 145 112 169 0 4 5 8 8 8 18 12 19 10 19 18 1 JJ 72 55 87 2J 22 33 61 111 667 0 140 120 700 770 840 800 950 1150 1200 2610 2820 2240 2410 2210 2090 2170 2290 2130 2960 2360 2 2 2 3060 228 1 34 33 32 38 51 39 35 36 94 36 69 50 50 50 87 83 41 41 40 48 4 135 1 1 1 1 7 1 3 6 17 19 10 18 10 16 Il 1 1 7 <1 <1 <1 <1 24 24 < < 38 J2 72 76 87 65 64 170 179 285 252 385 332 354 585 547 405 433 498 490 419 437 23J Il 20 22 24 29 22 22 31 31 33 30 30 39 30 32 36 36 58 46 45 35 145 32 36 51 39 50 59 lJ lJ 43 40 41 41 40 40 48 45 48 38 38 34 66 8 11 11 11 11 18 13 15 19 12 12 12 19 12 10 10 10 43 44 45 24 25 1 9 1.1 0.9 9.8 5.1 8.5 l.! 10.9 25.5 283 31.6 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5

208

Appendix G

Depth Correlation for Statistics

209

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 0.01 5.89 8.83 11.66 11.68 12.54 13.45 15.01 1.67 16.99 17.02 18.20 18.85 21.36 23.10 0.37 6.07 9.52 11.99 11.78 12.95 13.71 15.17 1.95 17.11 17.97 18.48 19.77 22.85 23.33 0.50 6.84 9.69 0.50 11.90 13.14 14.06 15.22 2.12 18.16 17.60 20.26 20.61 23.46 23.81 0.85 7.15 9.87 0.85 12.01 14.89 14.28 15.36 2.20 18.69 19.26 20.28 20.67 0.85 23.94 0.87 7.58 10.16 0.87 12.12 0.87 14.32 15.48 2.54 19.00 19.46 20.77 21.59 0.87 24.83 1.06 7.65 10.28 1.06 12.43 1.06 14.40 15.66 2.79 1.06 19.64 22.21 21.65 1.06 25.23 1.25 7.95 10.35 1.25 1.25 1.25 14.77 15.71 2.82 1.25 20.12 22.26 21.90 1.25 25.57 1.57 8.46 10.56 1.57 1.57 1.57 1.57 15.85 3.09 1.57 20.79 22.40 1.57 1.57 25.23 1.86 1.86 10.93 1.86 1.86 1.86 1.86 15.94 1.86 1.86 20.87 23.21 1.86 1.86 1.86 11.05 16.34 20.97 24.01 11.36

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 0.01 0.37 0.50 0.85 0.87 1.25 1.25 1.57 1.67 1.86 1.95 44.13 46.70 48.28 48.77 26.26 2.98 5.03 31.58 3.37 31.69 35.10 37.08 40.31 0.37 41.11 44.56 0.37 48.41 49.00 26.55 3.16 5.32 35.82 3.48 31.74 35.20 37.18 42.66 0.50 41.18 44.69 0.50 48.49 49.28 26.72 4.20 0.50 0.50 3.69 32.06 35.31 37.32 43.19 0.85 41.56 44.78 0.85 48.61 49.64 28.20 4.40 0.85 0.85 3.84 32.11 35.42 37.64 44.84 0.87 41.89 44.96 0.87 48.91 50.24 0.87 4.81 0.87 0.87 4.05 32.32 35.70 37.82 0.87 1.06 42.02 45.05 1.06 49.50 50.69 1.06 5.32 1.06 1.06 4.51 32.48 35.90 38.03 1.06 1.25 42.11 45.08 1.25 49.82 1.25 1.25 5.61 1.25 1.25 4.67 32.89 36.13 38.21 1.25 1.57 42.26 45.27 1.57 49.92 1.57 1.57 1.57 1.57 1.57 5.03 33.03 36.26 38.37 1.57 1.86 42.35 45.29 1.86 49.97 1.86 1.86 1.86 1.86 1.86 5.59 33.14 36.64 38.59 1.86 4.09 42.50 45.43 5.75 33.21 36.76 38.70 42.58 45.46 33.28 36.82 38.95 42.70 45.61 33.47 36.98 39.55 42.80 45.70 33.49 39.27 42.92 45.89 33.77 43.12 45.95 33.80 43.22 46.03 33.99 43.30 46.17 34.12 43.35 46.35 34.26 43.39 46.63 34.45 43.64 46.87 34.52 43.74 46.99 34.72 43.90 47.08

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34.92 44.05 47.24 44.18 47.37 44.34 47.49 47.81 47.91 47.98 48.04

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REFERENCES

Al Ali, J.R. and Abu-Salah, A.H., 1993, Exploration for Bentonite and Other Minerals in Azraq Depression: Natural Resources Authority (NRA), 4 Volumes.

Abed, A.M., Yasin, S., Sadaqa, R., and Al-Hawarl, Z., 2008, The paleoclimate of the eastern desert of Jordan during marine isotope stage 9: Quaternary Research, v. 69, p. 548- 468.

Abed, A., Carbonel, P., Collina-Girard, J., Fontugne, M., Petit-Marie, N., Reyss, J.C., and Yasin, S., 2000, Un paléolac du dernier interglaciaire pléistocène dans l’extrême-sud hyperaride de la Jordanie: Earth and Planetary Sciences, v. 330, p. 259-264.

Ahmad, K.I., 2010, Organic Geochemistry of Al-Azraq Basin, Jordan, An Interpretation of Paleoenvironment and Paleoclimate Using Bulk Organic Matter. Master Thesis. University of Missouri Kansas-City. 142 p.

Agrar, Hydrotechnik and GTZ, 1977, National Water Master Plan of Jordan: v. 8, Essenanover.

Alley, R.B., and Bender, M.I., 1998, Greenland ice cores: Frozen in time: Scientific American Magazine (2 February).

Al-Hunjul, N.G., 1995, The geology of Madaba area: Sheet no. 3153 II: The Hashemite Kingdom of Jordan, Ministry of Energy and Mineral Resources, Natural Resources Authority, Geology Directorate, Geological Mapping Division (Amman). 65 p.

Allen, J.L., and Thornley, D.M., 2004, Laser granulometry of Holocene estuarine silts: effects of hydrogen peroxide treatment: Holocene, v. 14, p. 290.295.

Al-Momani, T.M., 2000, Characterization, Industrial Utilization and Environmental Impact Of The Hiswa Clay Deposits, South Jordan. Ph.D. Thesis. University of Jordan.

Alonso-Zarza, A.M., 2003, Palaeoenvironmental significance of palustrine and calcretes in the geological record: Earth Science Reviews, v. 60, p. 261–298.

Alperin, M.J. and Reeburgh, W.S., 1985, Inhibition experiments on anaerobic methane Oxidation: Applied Environmental Microbial, v. 50, p. 940–945.

Al-Sayari, S.S., and Zötl, J.G., 1978, The Quaternary Period in Saudi Arabia: A cooperative research project of the University of Petroleum and Minerals, Dhahran, and the Austrian Academy of Sciences, Vienna, Springer-Verlag. 335 p.

Altabet, M.A., and Francois, R., 1994, Sedimentary nitrogen isotopic ratio as a recorder for surface ocean nitrate utilization: Global Biogeochemical Cycles, v. 8, p. 103–116.

212

Altabet, M.A., 1988, Variations in nitrogen isotopic composition between sinking and suspended particles: implications for nitrogen cycling and particle transformation in the open ocean: Deep-Sea Research, v. 35, p. 535–554. Ames, C.J., Nowell, A., Cordova, C.E., Pokines, J.T., and Bissoni, M.S., 2012, Paleoenvironmental Change and Settlement Dynamics in the Druze Marsh: results of recent excavation at an open-air Paleolithic site: Quaternary International (In Press).

Anderson, L., Abbott, M.B., and Finney, B.P., 2001, Holocene Climate Inferred from Oxygen Isotopes Ratios in Lake Sediments, Central Brooks Range, Alaska: Quaternary Research, v. 55, p. 313-321.

Andreola, F., Castellini, E., Manfredini, T., and Romagnoli, M., 2004, The role of sodium exametaphosphate in the dissolution process of kaolinite and kaolin: Journal of the European Ceramic Society, v. 24, p. 2113-2124.

Anoumenous1, Encyclopeda Britannica Facts Matter: Last excess 04-26-2013 http://www.britannica.com/EBchecked/topic/101353/celestine. Last access- 04/29/2013

Arens, N.C., Jahren, A.H., and Amundson, R., 2000, Can C3 plants faithfully record the carbon isotopic composition of atmospheric carbon dioxide? Paleobiology, v. 26, p. 137–164.

Ayed, R.A., 1996, Hydrology and Hydrogeology Study of the Azraq Basin, Jordan, Ph.D. Thesis, Department of Geology, University of Baghdad, Iraq.

Bar-Matthews, M., Ayalon, A., Matthews, A., and Hawkesworth, C.J., 2003, Sea–land oxygen isotopic relationships from planktonic foraminifera and speleothems in the Eastern Mediterranean region and their implication for paleorainfall during interglacial intervals: Geochimica et Cosmochimica Acta, v. 67, p. 3181–3199.

Bashkin, V.N, 2002, Modern Biogeochemistry: Kluwer Academic Publishers. p.561

Battarbee, W.R., Jones, V., Flower, R., Cameron, N., and Bennion, H., 2001, Diatoms, In: Smol, J., Birks, H., and Last, W., eds., Tracking Environmental Change Using Lake Sediments. Volume 3: Terrestrial, Algal and Siliceous Indicators: Dordrecht, Kluwer Academic Publishers, p. 155-202.

Battarbee, W.R, 1986, Diatom analysis, In: Handbook of Holocene Palaeoecology and Palaeohydrology. Ch.26: by Jone Wiley and Son Ltd. Edited by B. E. Berglund. 869 p.

Bayook, A, 1992, Batn El Ghoul Deposits as a Potential Source for Aluminum. Master Thesis, University of Jordan.

213

Beheiry, S.A., 1968-69, Geomorphology of central East Jordan: Bulletin de la Societe de Geographie d'Egypte, v. 41/42, p. 5-22.

Bender, F., 1974, Geology of Jordan, GebrderBorntrger, Berlin. p.196. Bender, F., 1975, Geology of the Arabian Pennisula, Geological Professional Paper 560-I, U.S. Department of the Interior, Washington D.C. 136 p.

Bentley, R.A., 2006, Strontium Isotopes from the Earth to the Archaeological Skeleton: A Review: Journal of Archaeological Method and Theory, v. 13, p. 135-187.

Bernasconi, S.M., Barbieri, A., and Simona, M., 1997, Carbon and nitrogen isotope variations in sedimenting organic matter in Lake Lugano: Limnology and Oceanography, v. 42. p.1755–1765

Bird Census Report, 2003, The Royal Society for the Conservation of Nature (RSCN). http://www.rscn.org.jo/RSCN/HelpingNature/ResearchforConservation/tabid/82/Defa ult.aspx.

Blatt, H., Middleton, G., and Murray, R., 1972, Origin of Sedimentary Rocks: Englewood Cliffs, New Jersey, Prentice-Hall, 634 p.

Bocherens, H., Billiou, Charpentier, V., and Mashkour, M., 2000, Palaeoenvironmental and archaeological implications of bone and tooth isotopic biogeochemistry (13C, 15N) in Southwestern Asia. In: H. Buitenhuis, M. Mashkour & F. Poplin Eds) Archaeozoology of the Near East IV, Groningen: ARC 32, v. B, pp. 104-115.

Bond, G., Showers, W., Cheseby, M., Lotti, R., Almasi, P., deMenocal, P., Priore, P., Cullen, H., Hajdas, I., and Bonani, G., 1997, A pervasive millennial-scale cycle in North Atlantic Holocene and Glacial climates: Science, v. 278, p. 1257–1266.

Boutton, T., 1991, Stable carbon isotope ratios of natural materials: II. Atmospheric, terrestrial, marine, and freshwater environments. In: Fry, B., ed., Isotope Techniques: San Diego, Academic Press, Inc., p. 173-185.

Boyle, J., 2001, Inorganic geochemical methods in palaeolimnology, In: Tracking Environmental Change Using Lake Sediments. Volume 2: Physical and Geochemical Methods (Last, M.L. & Smol, J.B., eds), Kluwer Academic Publishers, Dordrecht. p. 83-141.

Brauer, A., Dulski, P., Mangili, C., Mingram, J., and Liu, J. 2009, The potential of varves In high resolution paleolimnological studies: PAGE, v. 17, p. 96-98.

Brenner, M., Whitmore, T.J., Curtis, J.H., Hodell, D.A., and Schelske, C.L., 1999, Stable

214

isotope δ13C and δ15N signatures of historic lake trophic state: Journal of Paleolimnolimnology, v. 22, p. 205– 221.

Bright, J., 2006, Ostracod endemism in Bear Lake, Utah and Idaho. In: Paleoenvironments of Bear Lake, Utah and Idaho, and its catchment edited by Joseph G., Rosenbaum, Darrell S. Kaufman, 2009, The Geological Society of America.

Buchardt, B., and Fritz, P., 1980, Environmental isotopes as environmental and climatological indicators. In: Fritz, P., Fontes, J.Ch. (Eds.), Handbook of Environmental Isotope Geochemistry, Elsevier, Amsterdam. pp. 473–504.

Burdon, D.J., 1959, Handbook of the Geology of Jordan. Benham and Company Limited, Colchester, p. 82.

Burdon, D.J., 1982, Physiography. In: A.M. Quennell (ed.), Rift Valleys: Afro-Arabian. Hutchinson Ross Publishing Company, Stroudsberg. pp.355-364.

Calvert, S.E., Nielsen, B., and Fontugne, M.R., 1992, Evidence from nitrogen isotope ratios for enhanced productivity during formation of eastern Mediterranean sapropels: Nature, v. 359, p. 223–225.

Calvert, S., and Pederson, T., 1993, Geochemistry of Recent oxic and anoxic marine sediments: Implications for the geological record: Marine Geology, v. 113, p. 67–88.

Cane, G., 1992, A Paleoclimate reconstruction based on lacustrine sediments of the Azraq Basin, Jordan. Bachelor of Science Thesis. 104 p.

Campos, H.S., and Hallam, A., 1979, Diagenesis of English lower Jurassic limestones as inferred from oxygen and carbon isotope analysis: Earth and Planetary Science Letters, v. 45, p. 23-31.

Choudharry, P., , Routh, J., Chakrapani, G., Kumar,B., 2009, Biogeochemical records of paleoenvironmental changes in Nainital Lake, Kumaun Himalayas, India: Journal of Paleolimnology, v. 42, p. 571–586.

Choudharry, P., Routh, J., Chakrapani, G.J, 2009, An eoenvironmental record changes in sedimentary organic matter from Lake Sattal in Kumaun Himalayas, India: Science Total Environment, v. 407, p. 2783-2795.

Chang, Y., Yang, M., Nin, J., Fan, H., Lei, G., and Zhang, W., 2008, Sedimentation Geochemistry and Environmental Changes during the Late Pleistocene of Paleolake Qarhan in the Qaidam Basin: Journal of China University of Geosciences, v. 19, p. 1–8.

Cifuentes, L.A., Coffin, R.B., Solorzano, L., Cardenas,W., Espinoza, J., and Twilley, R.R.,

215

1996, Isotopic and elemental variations of carbon and nitrogen in a mangrove estuary. Estuar., Coast: Shelf Science, v. 43, p. 781–800.

Clark, I. D. and Fritz, P., 1997, Environmental Isotopes in Hydrogeology. New York, Lewis Publishers.

Cohen, A.S., 2003, Paleolimnology. New York, Oxford University Press. 500 p.

Cohen, A.S., and Thouin, C., 1987, Nearshore Carbonate Deposits in Lake Tanganyika: Geology, v. 15, p. 414-418.

COHMAP Members, 1988, Climatic changes of the last 18,000 years: observations and model simulations: Science, v. 241, p. 1043–1052.

Colman, S., 1996, Continental Drilling for Paleoclimatic Records: Recommendations from an International Workshop: PAGES Workshop Report Series, v. 96-4, p.104.

Coleman, D.C., and Fry, B., 1991, Carbon Isotope Techniques. San Diego, Academic Press. 274 p.

Committee on Sustainable Water Supplies in the Middle East. 1999, Water for the Future: The West Bank and Gaza Strip, Israel, and Jordan. Israel Academy of Sciences and Humanities; Palestine Academy for Science and Technology; Royal Scientific Society, Jordan; and the U.S. National Academy of Sciences, National Academy Press, Washington, D.C., 244 p.

Conley, D., 1998, An interlaboratory comparison for the measurement of biogenic silica in sediments: Marine Chemistry, v. 63, p. 39-48.

Cordova, E.C., 2007, Millennial Landscape Change in Jordan: Geoarchaeology and Cultural Ecology: Tucson, University of Arizona Press. 272 p.

Cordova, E.C., Nowell, A., Bisson, M.S., Ames, C.J.., Pokines, J., Chang, M., al-Nahar, M., 2012, Interglacial and Glacial Desert Refugia and the Middle Paleolithic of the Azraq Oasis, Jordan: Quaternary International (In Press).

Cordova, C.E., Nowell, A., Bisson, M., Pokines, J., Ames, C.J.H., al-Nahar, M., 2009, The Druze Marsh Paleolithic Project, North Azraq, seasons 2008 and 2009: stratigraphic sequences: Annual of the Department of Antiquities of Jordan, v. 53, p. 311-320.

Cordova, E.C., Rollefson, G.O., Kalchgruber, R., Wilke, P., and Quintero, L., 2008, Natural and cultural stratigraphy of ‘Ayn As-Sawda, Al-Azraq wetland preserve: 2007 excavation report and discussion of finds: Annual of the Department of Antiquities of Jordan, v. 52., p. 417-425.

216

Cotton, J., Sheldon, N., and Strömberg, C., 2012, High-resolution isotopic record of C4 photosynthesis in a Miocene grassland: Palaeogeography, Palaeoclimatology, Palaeoecology, v. 337–338, p. 88–98.

Craig, H., 1954, Carbon 13 in Plants and the Relationship between Carbon 13 and Carbon 14 Variations in Nature: The Journal of Geology, v. 62, p.115.

Criss, R.E.,1999, Principles of Stable Isotope Distribution. Oxford University Press. 254 p.

Cyr, A.J., 2004, Geochemical and isotopic evaluation of Fenghuoshan Group carbonates, North-Centeral Tibet. Implication for Paleoltimery of the Mid-Tertiary Plateau. Master Thesis. Miami University. Master thesis. 82 p.

Davies, C.P., 2007, Past Environments of the Jordan Plateau from the Paleolakes of the Eastern Desert. In: Crossing Jordan – North American Contributions to the Archaeology of Jordan. Eds. Levy, T.E., Daviau, P.M.M., Younker, R.W., and Shaer, M. Equinox Publishing, Ltd., Sheffield. pp. 79-86.

Davies, C.P., 2006, Quaternary paleohydrology and past climates of the Dhamar Highlands, Yemen: Quaternary Research, v. 66, p. 454-464.

Davies, C.P. 2005a, Past Environments of the Jordan Plateau from the Paleolakes of the Eastern Desert. In: Crossing Jordan – North American Contributions to the Archaeology of Jordan Eds. Levy, T.E., Daviau, P.M.M., Younker, R.W., and Shaer, M. Equinox Publishing, Ltd., pp. 79-86.

Davies, C.P., 2005b, Quaternary paleoenvironment and potential for human exploitation of the Jordan Plateau Desert Interior: Journal of Geoarchaeology, v. 20, p. 381-402.

Davies, C.P., 2000, Reconstruction of paleoenvironmentsfrom lacustrine deposits of the Jordan Plateau, Ph.D. dissertation, Tempe, AZ, Arizona State University, p. 278.

Davis, S., Wiegand, B., Carroll, A., and Chamberlain, P., 2008, The effect of drainage reorganization on paleoaltimetry studies: An example from the PaleogeneLaramide foreland: Earth and Planetary Science Letters, v. 275, p. 258–268.

Das, M.P., Devaraj, H., Poeta. M., Hickman, J.J., 2003, Electrophysiological and morphological characterization of rat embryonic motoneurons in a defined system: Biotechnology Progress, v. 19, p.1756–1761.

Dean, W.E., 1999, The carbon cycle and biogeochemical dynamics in lake sediments: Journal of Paleolimnology, v.21, p. 375-393.

Dean, W.E., and Schwalb, A. 2000, Holocene environmental and climatic changes in the Northern Great Plains as recorded in the geochemistry of sediments in the Pickerel

217

Lake, South Dakota: Quarternary International, v. 67, p. 5-20.

Deocampo, D.M., 2010, The geochemistry of continental carbonates. In: Alonso-Zarza, A.M., Tanner, L.H. (Eds.), Carbonates in Continental Settings: Geochemistry, Diagenesis and Applications: Developments in Sedimentology, v. 26, p. 1–45.

Dickson, J.D., and Coleman, M.L., 1980, Changes in carbon and oxygen isotope composition during limestone diagenesis: Sedimentology, v. 27, p. 107-118.

Didyk, B.M., Simoneit, B.T., Brassell, S.C. and Eglinton, G. 1978. Organic geochemical indicators of paleoenvironmental conditions of sedimentation. Nature, v. 272, p. 216 – 222.

Dong,G., Xia, Z., Elston, R., Sun, X., and Chen F., 2009, Response of geochemical records in lacustrine sediments toclimate change and human impact during middle Holocene in Mengjin, Henan Province, China. Front: Earth Science China, v. 3, p. 279–285.

Drummond, C.N., Wilkinson, B.H., and Lohmann, K.C., 1993, Rock-dominated diagenesis of lacustrine magnesian calcite micrite: Carbonates and Evaporites, v. 8, p. 214-223.

Dutkiewicz, A., Herczeg, A.L., and Dighton, J.C., 2000, Past changes to isotopic and solute balances in a continental playa: clues from stable isotopes of lacustrine carbonates: Chemical Geology, v. 165, p. 309-329.

Eardley, A.J., 1966, Sediment of Great Salt lake: Utah American Associated of petroleum Geologists Bulletin, v.21, p. 1305-1411.

Edgell, H.S., 2006, Arabian deserts: nature, origin and evolution. Dordrecht: Springer. 592 p.

Eicher, U., and Siegenthaler, U., 1976, Palynological and oxygen isotope investigations on Late-Glacial sediment cores from Swiss lakes: Boreas, v. 5, p. 109-117.

Epstein, S., Buschbaum, R., Lowenstam, H. and Urey, H.C., 1951, Carbonate-water isotopic temperature scale: Geology, v. 62, p. 417-426.

Eugster, H., and Kelts, K., 1983, Lacustrine chemical sediments. In: A.S. Goudie and K. Pye (Editors), Chemical Sediments and Geomorphology, Academic Press, London, p 321- 368.

Faure, G., 1991, Principle and application of inorganic geochemistry. Third Edition. Macmillan Publishing Company. 626 p.

Faure, K., de Wit, M.J., and Willis, J.P., 1995, Late Permian global coalhiatus linked to 13C- depleted CO2 flux into the atmosphere during the final consolidation of Pangea: Geology, v. 23, p. 507-510

218

Filippi, M.L., and Talbot, M.R., 2005, The palaeolimnologyof northern Lake Malawi over the last 25 ka based upon the elemental and stable isotopic composition of sedimentary organic matter: Quaternary Science Reviews, v.24, p. 1303-1328.

Fitzsimmons, K., Cohen, T., Hesse, P., Jansen, J., Nanson, G., May, Jan- Hendrik, Barrows, T., Haberlah, D., Hilgers, A., Kelly, T., Larsen, J., Lomax, J., and Treble, P., 2012, Late Quaternary palaeoenvironmental change in the Australian drylands: Quaternary Environment Review. In press, corrected Proof.

Fleitmann, D., Burns, S., Neff, U., Mangini, A., and Matter, A., 2003, Changing moisture sources over the last 330,000 years in Northern Oman from fluid inclusion evidence in speleothems: Quaternary Research, v. 60, p. 223–232.

Flugel, E., 2010, Microfacies of carbonate rocks: analysis, interpretation and application. Springer. 983 p.

Fogel, M., Tuross, N., Johnson, B., and Miller, G., 1997, Biogeochemical record of ancient humans: Organic Geochemistry, v. 27, p. 275–287.

Fontugne, M.R., and Calvert, S.E., 1992, Late Pleistocene variability of the carbon isotopic composition of organic matter in the eastern Mediterranean: monitor of changes in carbon sources and atmospheric CO2 concentrations: Paleoceanography, v. 7, p. 1–20.

Friedman, G.M., 1978, Solar Lake: a sea-marginal pond of the Red Sea (Gulf of Aquaba, Elat) in which algal mats generate carbonate particles and laminites. In: Krumbein, W.E. (Ed.), Environmental Environmental Biogeochemistry and Geomicrobiology, The Aquatic Environment. Wiley, Ann Arbor, MI, pp. 227–235.

Friedman, I. and O’Neil, J.R., 1977, Compilation of stable isotope fractionation factors of geochemical interest. Data of geochemistry. K. K. Chapter. Washington DC, USGS. Paper 440-kk [4-5, 6-2].

Garrard, A., 1998, Environment and cultural adaptations in the Azraq Basin, 24-7,000 B.P. In: The Prehistoric Archaeology of Jordan, D. Henry, D., ed. Oxford, British Archaeological Reports International Series, v. 705, p. 139-148.

Gasse, F., 2000, Hydrological changes in the African tropics since the Last Glacial Maximum: Quaternary Science Reviews, v. 19, p. 189-211.

Garfunckel, Z., 1997, The history and formation of the Dead SeaBasin. In: Niemi, T.M., Ben-Avraham, Z., Gat, J.R. (Eds.), The Dead Sea; The Lake and Its Settings. Oxford Monographs on Geology and Geophysics, vol. 36. Oxford University Press, New York, pp. 36–56.

219

Gibert, R., Taberner, C., Sáez, A., Giralt, S., Alonso, R.N., Edwards, R.L., and Pueyo, J.J., 2008, Igneous origin of CO2 in ancient and recent hot-spring waters and travertines from the Argentinean Andes: Journal of Sedimentary Research, v. 79, p. 554–567.

Goldstein, J., Newbury, D, Joy, D., Lyman, C., Echlin, P., Lifshin, E., Sawyer, L., and Michael, J., 2003, Third Edition. Springer Science Business Media Inc. 689 pp.

Goñi, M.A., Ruttenberg, K.C., and Eglinton, T.I.,1998, A reassessment of the sources and importance of land-derived organic matter in surface sediments from the Gulf of Mexico: Geochimica Cosmochimica Acta Journal, v. 62, p. 3055–3075.

Graham, M.C., Eaves, M.A., Farmer, J.G., Dobson, J., and Fallick A.E., 2001, A study of carbon and nitrogen stable isotope and elemental ratios as potential indicators of source and fate of organic matter in sediments of the Forth Estuary, Scotland: Estuar Coast Shelf Science, v. 51, p.375–380.

Gorham, E., 1991, Biogeochemistry: Its Origins and Development: Biogeochemistry, v. 13, p. 199-239.

Gorham, E., 1991, Northrenpeatlands: Role in the carbon cycle and probable responses to climatic warming: Ecology Application, v. 1, p. 182-195.

Grocke, E., 1998, Carbon isotope analysis of fossil plants as a chemostratigraphic and paleoenvironmental tool: Lethaia, v. 31, p. 1-13.

Grocke, D.R., Hesselbo, S.P., and Jenkyns, H.C., 1999, Carbone isotopic composition of lower Cretaceous fossil wood: Ocean atmosphere chemistry and relationship to sea- level Change: Geology, v. 27, p. 155-158.

Gustavson, T.C., Holliday, V.T., and Hovorka, S.D., 1995, Origin and development of Playa Basin, sources of recharge to the Ogallala Aquifer, southern high plain, Taxas and New Mecxico. Bureau of Economic Geology Report of Investigation 229, The University of Texas Austin. 44 p.

Halley, R.B., 1976, Chapter 8.5 Textural variation within Great Salt Lake algal mounds: Developments in sedimentology Elsevier, v.20 , p. 435–46.

Hammarlund, D., and Buchardt, B. 1996, Composite stable isotope records from a Late Weichselian lacustrine sequence at Grange, Lolland, Denmark: evidence of Allerod and Younger Dryas environments: Boreas. v. 25, p. 8-22.

Hammarlund, D., Bjorck, S., Buchardt, B., and Thomsen, 2005, Limnic responses to increased effective humidity during 8200 cal. yr BP cooling event in southern Sweden: Journal of Paleolimnology, v. 34, p. 471-480.

220

Haug, G.H., Pedersen, T.F., Sigman, D.M., Calvert, S.E., Nielsen, B., and Peterson, L.C., 1998, Glacial/interglacial variations in production and nitrogen fixation in the Cariaco Basin during the last 580 kyr: Paleoceanography., v.13, p.427-450

Hayter, E. and Pakala, C., 1989, Transport of inorganic contaminants in estuarial water: Journal of Coastal Research, v. 5, p. 217-230.

Heiri, O., Lotter, A., and Lemcke, G., 2001, Loss on ignition as method for estimating organic and carbonate content in sediments: reproducibility and comparability of results: Journal of Paleolimnology, v. 25, p. 101-110.

Herczeg, L., 1988, Early diagensis of organic matter in lake sediments: a stable carbon isotope study of pore waters: Chemical Geology (Isotope Geoscience Section), v. 72, p. 199-209.

Herczeg, A.L., Smith, A.K., and Dighton, J.C., 2001, A 120 year record of changes in nitrogen and carbon cycling in Lake Alexandrina, South Australia: C:N, d15N, and d13C in sediments: Applied Geochemistry, v. 16, p. 73–84.

Hickey, C., and Gibbs, M., 2009, Lake sediment phosphorus release management— Decision support and risk assessment framework: New Zealand Journal of Marine and Freshwater Research, v. 43, p. 819-856.

Hill, T. and Lewicki, P., 2006, Statistics: methods and applications a comprehensive reference for science, industry, and data mining: StatSoft Inc., Tulsa, OK, 831p.

Hines, M., Lyones, W., Lent, R., and Long, D., 1992, Sedimentary biogeochemistry of an acidic, saline groundwater discharge zone in Lake Tyrrell, Victoria, Australia: Chemical Geology, v. 96, p. 53-64.

Hodgson, P.E., Gadioli, E., and Gadioli E.E., 1997, Introductory Nuclear Physics. Oxford, Clarendon Press.

Hollander, D.J., and McKenzie, J.A., 1991, CO2 control on carbon isotope fractionation during aqueous photosynthesis: a paleo-pCO2 barometer: Geology, v. 19, p. 929–932.

Horton, W., Horton, Chamberlain, P., Fantle, M., and Blum, D., 1999, Chemical weathering and lithologic controls of water chemistry in a high-elevation river system: Clark’s Fork of the Yellowstone River, Wyoming and Montana: Water Resources Research, v. 35, p. 1643-1655.

Houyun, Z., and Zhaoyu, Z., 2002, Oxygen isotopic composition of lacustrine carbonates since 130Ka BP from a Tianshuihai Lake core, Tibet: an overall increasing delta18O trend and its implications: Journal of Asian Earth Sciences, v. 20, p. 225-229.

221

Ibrahim, K., 1996, The Regional Geology of Al Azraq: Amman, Jordan, Geological Mapping Division, Natural Resources Authority, p. 67.

Imbrie, J., Hays, J.D., Martinson, D.G., McIntyre, A., Mix, A.C., Morley, J.J., Pisias, N.G., Prell, W.L., and Shackleton, N.J., 1984, The orbital theory of Pleistocene climate: support from a revised chronology of the marine d18O record: In: Berger, A.L., Imbrie, J., Hays, H., Kukla, G., and Saltzman, B., (Eds.), Milankovitch and Climate: Understanding the Response to Astronomical Forcing: Proceedings of the NATO Advanced Research workshop held 30 November–4 December, 1982 in Palisades, NY: Dordrecht, The Netherlands, D. Reidel Publishing, pp. 269–305.

Indermuhle, A., Stocker, T.F., Fischer, H., Smith, H.J., Wahlen, M., Deck, B., Mastroianni, D., Tschumi, J., Blunier, T., Meyer, R., and Stauffer, B., 1999, Holocene carbon-cycle dynamics based on CO2 trapped in ice at Taylor Dome, Antarctica: Nature, v. 398, p.121–126.

Ito, E., 2001, Application of stable isotope techniques to inorganic and biogenic carbonates. In: Last, W.M., Smol, J.P. (Eds.), Tracking Environmental Change Using Lake Sediments, Physical and Geochemical Techniques, vol. 2. Kluwer Academic Publishers, Dordrecht, The Netherlands, pp. 351– 371.

Jones, M.D. and Richter, T. 2011, Paleoclimatic and archeological implications of Pleistocene and Holocene environments in Azraq, Jordan. Quaternary Research, v.76, p. 363-372.

Knudson, K.J., 2011, Chapter In Identifying Archaeological Human Migration Using Biogeochemistry. In: Rethinking Anthropological Perspectives on Migration by Cabana, Graciela and Clark, Jeffery. University of Florida Press, p. 362.

Keelley, J.E., Sandquist, D.R., 1992, Carbon: Fresh water plants: Plant Cell Environment, v.15, p. 1021-1035.

Killops S. and Killops V., 1993, An Introduction to Organic Geochemistry: UK, Longman Scientific and Technical.

Krumbein, W.E, and Cohen, Y., 1974, Biogene, Klastische and Evaporitische Sedimentation in einem mesothermen monomiktischen ufernahen See (Golf von Aqaba): Geology Rdsch, v.63, p. 1035-1965.

Kim, J., Furukawa, Y., Dong, H., and Newell, S., 2005, The effect of microbial Fe(III) reductionn on smectite flocculation. Clay: Clay Minerals, v. 53, p. 572-579.

Kirby, M.E., Poulsen, C.J., Lund, S.P., Patterson, W.P., Reidy, L., and Hammond, D.E., 2004, Late Holocene lake level dynamics inferred from magnetic susceptibility and stable oxygen isotope data: Lake Elsinore, southern California (USA): Journal of

222

Paleolimnology, v.31, p. 275-293.

Koch, L, Zachos, C., and Ginerich, 1992, Correlation between isotope records in marine and continental carbon reservoirs near the Palaeocene boundary: Nature, v. 358, p. 319- 322.

Kristensen, E., Jensen, M.H., and Andersen, T.K., 1985, The impact of polychaete (Nereisvirens Sars) burrows on nitrification and nitrate reduction in estuarine Sediments: Journal of Experimental Marine Biology and Ecology, v.85, p.75-91.

Kroon D., Alexander I., Little M., Lournes L. J., Matthewson A., Robertson A. H. F. and Sakamoto T., 1998, Oxygen isotope and sapropel stratigraphy in the Eastern Mediterranean during the last 3.2 million years: Proc. ODP, v. 160, p. 181–189.

Ku, H.W., Chen, Y.G., Chan, P.S., Liu, H.C., and Lin, C.C., 2007, Paleo-environmental evolution as revealed by analysis of organic carbon andnitrogen: A case of coastal Taipei Basin in Northern Taiwan: Geochemical Journal, v. 41, p. 111-120.

Kuhry and D.H., Vitt, 1996, Fossil Carbon/Nitrogen Ratios as a Measure of Peat Decomposition: Ecology, v. 77, p.271–275.

Larrasoana, J., Roberts, A., Rohling, E., Winklhofer, M., and Wehausen, R., 2003, Three million years of monsoon variability over the northern Sahara: Climate Dynamics, v. 21, p. 689–698.

Lamb, A.L., Wilson, G.P. and Leng, M.J., 2006, A review of coastal palaeoclimate and relative sea-level reconstruction using δ13C and C/N ratios in organic material: Earth- Science Reviews, v. 75, p. 29-57.

Last, W.M., 2001, Mineralogical analysis of lake sediments, In: Tracking Environmental Change Using Lake Sediments. Volume 2: Physical and Geochemical Methods (Last, W.M. & Smol, J. B., eds), p. 143-187. Kluwer Academic Publishers, Dordrecht.

Last, W.M., and Smol, J.P., 2001, Tracking Environmental Change Using Lake Sediments.Dordrecht, Kluwer Academic Publishers. 504 p.

Leng, M.J., 2006, Isotopes in Palaeoenvironemental research. Volume 10. Springer. 307 p.

Leng, M.J., and Marshall, J.D., 2004, Palaeoclimate interpretation of stable isotope data from lake sediment archives: Quaternary Science Reviews, v. 23, p. 811 – 831.

Letolle, R., 1980, Nitrogen- 15 in the natural environment. In: Fritz P & Fontes JC (Ed) Handbook of Environmental Isotope Geochemistry. p.407-433). Elsevier, Amsterdam.

223

Lezine, A., Salie, J., Robert, C., Wertz, F., and Inizan, M., 1998, Holocene Lakes from Ramlat as-Sab’atayn (Yemen) Illustrate the Impact of Monsoon Activity in Southern Arabia: Quaternary Research, v.50, p. 290–299.

Li, G., Chen, J., and Chen, Y., 2013, Primary and secondary carbonate in Chinese loessdiscriminated by trace element composition: Geochimica Cosmochimica Acta Journal, v. 103, p. 26–35.

Li, H.C., and Ku, T.L., 1997, δ13C - δ18O covariance as a paleohydrological indicator for closed-basin lakes: Palaeogeography Palaeoclimatology Palaeoecology, v.133, p.69- 80.

Lister, G., Kelts, K., Chen, K.Z., Yu, J.Q. and Niessen, F., 1991, Lake Qinghai, China: closed-basin lake levels and the oxygen isotopic record for ostracoda since the latest Pleistocene: Palaeogeography, Palaeoclimatology, Palaeoecology, v. 84, p.141-162.

Liutkus, C.M., and Wright, J.D., 2008, The influence of hydrology and climate on the isotope geochemistry of playa carbonates: a study from Pilot Valley, USA: Sedimentology, v. 55, p. 965–978.

Liutkus, C., Wright, J., Ashley, G., and Sikes, N., 2005, Paleoenvironmental interpretation of lake-margin deposits using d13C and d18O results from early Pleistocene carbonate rhizoliths, Olduvai Gorge, Tanzania: Geology. v. 33, p. 377– 380.

Lohse, K, Brooks, Paul , McIntosh, Jennifer C., Meixner, Thomas, and Huxman, Travis, 2009, Interactions Between Biogeochemistry and Hydrologic Systems: Annual Review of Environment and Resources, v. 34, p. 65-96.

Lyle, A., and Lyle, M., 2002, Determination of biogenic opal in pelagic marine sediments: a simple method revisited. In: Proceedings of the Ocean Drilling Program, Initial Reports. Volume 199 (Lyle, M., Wilson, P. A., Janecek, T. R., eds), pp. 1-21. College Station, TX (Ocean Drilling Program).

Machado, M.J., Perez-Gonzalez, A., and Benito, G., 1997, Paleoenvironmental changes during the last 4000 yr in the Tigray, Northern Ethiopia: Quaternary Research, v. 49, p. 312–321.

Mackenzie, F.T., 2009, Global Biogeochemical Cycles and the Physical Climate System. Published University Corporation for Atmospheric Research. p.69

Madanat, M., Mehyar, N., and Zurquiah, N., 2006, Silica Sands. Geological Survey Administration.Mineral Status and Future Opportunity: Natural Resources Authority (NRA).

224

Martin-Puertas, C., Valero-Garce´s, B., Mata, P., Moreno, A., Giralt, S., Martıńez-Ruiz, F., and Jimeńez-Espejo, F., 2011, Geochemical processes in a Mediterranean Lake:a high-resolution study of the last 4,000 years in Zonãr Lake, southern Spain: Journal of Paleolimnology, v. 46, p.405–421.

MATLAB 8.0 The MathWorks, Inc., Natick, Massachusetts, United States.

Matthews, A., and Katz, A., 1977, Oxygen isotope fractionation during dolomitization of calcium carbonate: Geochimica Cosmochimica Acta Journal, v.41, p.1431-1438.

Matson, E.A., and Brinson, M.M., 1990, Stable carbon isotopes and the C:N ratio in the estuaries of the Pamlico and Neuse Rivers, North Carolina: Limnology. and Oceanography, v. 35, p. 1290–1300.

Mayer, B., and Schwark, L., 1999, A 15,000-year stable isotope record from sediments of Lake Steisslingen,Southwest Germany: Chemical Geology, v.161, p. 315-337.

McCave, I., and Syvitski, J., 1991, Principles and methods of particle size analysis. In: J.P.M. Syvitski (ed.), Principles, Methods, and Applications of Particle Size Analysis, New York, Cambridge University Press, p. 3-21.

McClelland, J.W., Valiela, I., and Michener, R.H., 1997, Nitrogen-stable isotope signatures in estuarine food webs: A record of increasing urbanization in coastal watersheds: Limnology and Oceanography. v. 42, p. 930-937.

McClure, H., 1976, Radiocarbon chronology of the late Quaternary lakes in the Arabian Desert: Nature, v. 263, p.755–756.

McCrea, J. M., 1950, On the Isotopic Chemistry of Carbonates and a Paleotemperature Scale: Journal of Chemical Physics, v. 18, p. 849-858

McFadden, M., Patterson, M.T., and Anderson, W. 2005, Multi-proxy approach to long- and short-term Holocene climate-change: evidence from eastern Lake Ontario: Journal of Paleolimnology, v. 33 p. 371-391.

McFadden, M.A., Patterson, W.P., Mullins H.T., and Anderson, WT., 2005, Multi-proxy approach to long- and short-term Holocene climate-change: evidence from eastern Lake Ontario: Journal of Paleolimnology, v. 33, p. 371-391.

McFadden, M., Patterson, W., and Williams, A., 2004, Paleoproductivity of eastern Lake Ontario over the past 10,000 years. Limnology and Oceanograaphy, v. 49, p.1570-1581.

Meissner, R., 1989, Rupture, Creep, lamellae and crocodiles: Happening in the continental crust: Terra Nova, v. 1, p.17-28.

225

Meyers, P.A., 2003, Applications of organic geochemistry to paleolimnological reconstructions: a summary of examples from the Laurentian Great Lakes: Organic Geochemistry, v.34, p.261-289.

Meyers, P.A., 1997, Organic geochemical proxies of paleoceanographic, paleolimnologic, andpaleoclimatic processes, Organic Geochemistry, v. 27, p. 213–250.

Meyers, P.A., 1994, Preservation of elemental and isotopic source identification of sedimentary organic matter: Chemical Geology, v. 114, p. 289-302.

Meyers, P.A., 1993, Preservation of elemental and isotopic source identification of sedimentary organic matter: Chemical Geology, v. 114, p. 289-302

Meyers, P.A., and Ishiwatari, R.,1993, The early diagenesis of organic matter in lacustrine sediments. In: Engels, M. and Macko, S., eds., Organic Geochemistry: Principles and Applications, New York, Plenum Press, p. 185-209.

Meyers, P.A., Leenheer, M.J., and Bourboniere, R.A., 1995, Diagenesis of vascular plant organic matter components during burial in lake sediments: Aquatic Geochemistry, v. 1, p. 35–52.

Meyers P.A., and Teranes, J., 2001, Sediment organic matter. In: Last, W. and Smol J., eds., Tracking Environmental Change Using Lake Sediments: Volume 2: Physical and Geochemical Techniques: Dordrecht, The Netherlands, Kluwer Academic Publishers, p.239-269.

Meyers, P.A., and Lallier-Verge, E., 1999, Lacustrine sedimentary organic matter records of Late Quatemarypaleoclimates: Journal of Paleolimnology, v. 21, p. 345–372.

Mikutta, R., Kleber, M., Kaiser, K., and Jahn, R. 2005, Review: removal of organic matter from soils using hydrogen peroxide, sodium hypochlorite and disodium peroxodisulfate: Soil Science Society of America Journal, v. 69, p. 120.135.

Moh’d, B., K., 1986, The Geology of Wadi Al Buway’ija, Map Sheet No. 3251 IV. Geological Mapping project, Natural Resources Authority, Hashemite Kingdom of Jordan, Amman: Bulletin, v. 5, p. 46.

Müller, G., Irion, G., and Forstner, U., 1972, Formation and diagenesis of inorganic Ca-Mg carbonates in the lacustrine environment: Naturwissenschaften, v. 59/4, p. 158-164.

Monica, A.S., and Carlos, E.R., 2002, Behavior of selected micro and trace elements and organic matter in sediments of a freshwater system in south-east Brazil: The Science of the Total Environment, v. 292, p. 121–128.

226

Murray, M., 2002, Is laser particle size determination possible for carbonate- rich lake Sediments: Journal of Paleolimnology, v. 27, p. 173-183.

Muzuka, A., Ryner, M., and Holmgren, K., 2004, 12,000-Year, preliminary results of the stable nitrogen and carbon isotope record from the Empakai Crater lake sediments, Northern Tanzania: Journal of African Earth Sciences, v. 40, p. 293–303.

Muzuka, A., 2006, Sable isotopes composition of organic carbon and lacustrine sediments from sub-arid Northern Tanzania: Tanzania Journal of science, v. 32, p. 61-74.

Nakatsuka, T., Handa, N., Harada, N., Sugimoto, T., and Imaizumi, S., 1997, Origin and decomposition of sinking particulate organic matter in the deep water column inferred from the vertical distributions of its δ15N, δ13C and δ14C: Deep-Sea Research, Part 1. v. 44, p. 1957–1979.

Naqa, Ali, 2010, Study off salt water intrusion in the Upper Aqufer in Azraq Basin, Jordan. FinalReport. IUCN.

Neev, D., Emery, K.O., 1995, The destruction of Sedom, Gomorrah, and Jericho. Oxford University Press. 175 p.

Nicholes, G., 2009, Sedimentology and Stratigraphy. Second Edition.Willey-Blackwell. pp. 419.

North Jordan Water Resources Investigation Project (NJWRIP), Azraq Basin Water Resources Study, Draft Final Report, Water Resources Department, Water Authority, Jordan 1989.

O'Leary, M., Madhavan, S., and Paneth, P., 1992, Physical and chemical basis of carbon isotope fractionation in plants: Plant, Cell, and Environment, v. 15, p. 1099-1104.

O’Leary, M.H., 1989, Multiple isotopes effects on enzyme-catalyzed reaction: Review Biochemistry, v. 58, p. 377-401

O’Leary, M.H., 1988, Carbon Isotope in Photosynthesis: Bioscience, v.38, p. 328-336.

Orem, W., and Kotra, R., 1997, The role of biogeochemistry USGS sediment research: Proceedings of the U.S. Geological Survey (USGS) Sediment Workshop: February 4-7, 1997.

O’Sullivan, P., 2004, Paleolimnology.The Lakes Handbook.P. E. O’Sullivan and C. S. Reynolds: Oxford, Blackwell Science, v. 1, p. 609-666.

Palanques A, Sanchez-Cabeza J.A., Masque P, and Leon L, 1998, Historical record of heavy

227

metals in a higly contaminated Mediterranean deposit: the Besosprodelta: Marine Chemistry, v.61, p. 209–217.

Parker, A., Davies, C., and Wilkinson, T., 2006, The Early-Mid Holocene Moist Period in Arabia: Some Recent Evidence fromLacustrine Sequences in Eastern and Southwestern Arabia: Proceedings of the Seminar for Arabian Studies, v. 36, p. 243- 255.

Paterson, D., 1997, Biological mediation of sediment erodibility: ecology and physical dynamics. In: Cohesive Sediments (Burt, N., Parker, R. and Watts, J., eds), p. 215-229. John Wiley and Sons, Chichester.

Pattan, J.N., Parthiban, G., Gupta, S.M., and Mir, I.A., 2012, Fe speciation and Fe/Al ratio in the sediments of southeastern Arabian Sea as an indicator of climate change: Quaternary International., v. 250, p. 19-26

Paz, J., and Rossetti, D., 2006, Paleohydrology of an Upper Aptian lacustrine system from northeastern Brazil: Integration of facies and isotopic geochemistry: Palaeogeography, Palaeoclimatology, Palaeoecology, v. 241, p.247–266.

Peters, E., Sweeney, E., and Kaplan, R., 1978, Correlation of carbon and nitrogen stable isotope ratios in sedimentary organic matter: Limnology and Oceanography, v. 23, p. 598–604.

Petersen, B.J., and Howarth, RW., 1987, Sulfur, Carbon, and Nitrogen Isotopes Used to Trace Organic Matter Flow in the Salt-Marsh Estuaries of Sapelo Island, Georgia: Limnology and Oceanography, v. 32, p. 1195- 1213.

Petit-Maire, N., Sanlaville, P., Abed, A.M., Yasin, S., Bourrouilh, R., Carbonel, P., Fontugne, M., Reyss, J., 2002, New data for an Eemian lacustrine phase in Southern Jordan: Episodes, v. 25, p. 279-280.

Petit-Maire, N., Carbonel, P., Reyss, J.L., Sanlaville, P., Abed, A., Bourrouilh, R., Fontugne, M., Yasin, S., 2010, A vast Eemian paleolake in southern Jordan (29_ N): Global and Planetary Change, v. 72, p. 368-373.

Petraglia, M.D., Alsharekh, A.M., Crassard, R., Drake, N.A., Groucutt, H., Parker, A.G., and Roberts, R.G., 2011, Middle Paleolithis occupation on a Marine Isotope Stage 5 lakeshore in the Nafud Desert, Saudi Arabia: Quaternary Science Reviews, v. 30, p. 1555-1559.

Pancost, R.D., and Boot, C.S., 2004, The palaeoclimatic utility of terrestrial biomarkers in marine sediments: Marine Chemistry, v. 92, p. 239–261.

Poppe, L., and Polloni, C., 2000, USGS East-Coast Sediment Analysis: Procedures,

228

Database, and Georeferenced Displays, U.S. Geological Survey Open-File Report 00- 358, CD-ROM.

Poulson, S., and John, B., 2003, Stable isotope and trace element geochemistry of the Basal Bouse Formation carbonate, southwestern United States: Implications for the Pliocene uplift history of the Colorado Plateau. GSA Bulletin: v. 115, p. 434–444.

Powell, J.H., 1989, Stratigraphy and Sedimentation of the Phanerozoic Rocks in Central and Southern Jordan Part A Ram and Khreim Groups: Geological Bulletin, Jordan 1:50000 Geological Mapping Series No. 11, p. 76.

Pueyo, J.J., Sáez, A., Giralt, S., Valero-Garcés, B.L., Moreno, A., Bao, R., Schwalb, A., Herrera, C., Klosowska, B., and Taberner, C., 2011, Carbonate and organic matter sedimentation and isotopic signatures in Lake Chungará, Chilean Altiplano, during the last 12.3 kyr: Palaeogeography, Palaeoclimatology, Palaeoecology, v. 307, p. 339–355.

Rahaman,W., Singh, S., Sinha, R., and Tandon, S, 2011, Sr, C and O isotopes in carbonate nodules from the Ganga Plain: Evidence for recent abrupt rise in dissolved 87Sr/86Sr ratios of the Ganga: Chemical Geology, v. 285, p. 184–193.

Rains, M.C., Graham E.F., Harter, T., Randy A.D., and Robert J.W., 2013, The role of perched aquifers in hydrological connectivity and biogeochemical processes in vernal pool landscapes, Central Valley, California: Hydrological Processes, (in press).

Rasmussen, P., and Anderson, N.J., 2005, Natural and anthropogenic forcing of aquatic macrophyte development in a shallow Danish lake during the last 7000 years: Journal of Biogeography, v. 32, p. 1993-2005.

Rau, G., 1978, Carbon-13 depletion in a subalpine lake: Carbon flow implications: Science, v. 201, p. 901–902.

Reeburgh, W., 1989, Coupling of the carbon and sulphur cycles through anaerobe methane oxidation. New York, N.Y: John Wiley & Sons.

Renaut, R., and Last, W.M., 1994, Salt lake sedimentology and geochemistry: introduction and historical perspective: In: Sedimentology and Geochemistry of Modern and Ancient Saline Lakes. Renaut, R. and Last, W. eds., Tulsa, Society for Sedimentary Geology, Special Publication No. 50.

Risacher, F., and Eugster, H.P., 1979, Holocene pisloliths encrustations associated with spring-fed surface pools, Pastos Grandes, Bolivia: Sedimentary, v. 26, p. 253-270.

Roberts, J., Jepsen, R., Gotthard, D., and Lick, W., 1998, Effects of particle size and bulk

229

density on erosion of quartz particles: Journal of Hydraulic Engineering., v. 124, p. 1261-1267.

Roberts, N., Taieb, M., Barker, P., Damnati, B., Icole, M., Williamson, D., 1993, Timing of the Younger Dryas event in East Africa from lake-level changes. Nature v. 366, p. 146–148.

Rodrigues, T., Voelker, A.H.L., Naughton, F., Grimalt, J.O., and Abrantes, F.A., 2012, Past climate variability in the Iberian Margin during Marine Isotope Stages 15-9 (570 to 300 ka): Suborbital glacial variability and interglacial stability. EGU General Assembly 2012, published abstract, April 22-27, 2012, Vienna, Austria, p. 10876.

Rollefson, G.O., 2000. Ain el-Assad (Lion Spring) revisited, 1996, The Azraq Acheulian in situ. In: Stager, L., Greene, J., and Coogan, M., eds., The Archaeology of Jordan and Beyond: Essays in Honor of James A. Sauer, Winona Lake, Eisenbrauns, p. 418-428.

Rollefson, G., Schnurrenberger, D., Quintero, L. Watson, R.P., Low, R., 1997, Ain Sodann d’Ayn asuya: New late Pleistocene and Early Holocene sites in the Azraq Shishanarea, eastern Jordan. In: Gebel, H.K., Kafafi, Z., Rollefson, G.O., (Eds.), The prehistory of Jordan II. Perspectives from 1997. Ex Oriente, Berlin, pp. 45–58.

Rosen, M.R., Turner, J.V., Coshell, L., and Gailitis, V., 1995, The effect of water temperature, stratification, and biological activity on the stable isotopic composition and timing of carbonate precipitation in a hypersaline lake: Geochimica osmochimica Acta Journal, v. 59, p. 979-990.

Rosenbaum, J., and Sheppard, S.M.F., 1986, An isotopic study of siderites, dolomites and ankerites at high temperatures. Geochimica osmochimica Acta Journal, v. 50, p.1147–1150.

Routh, J., Choudhary , P., Meyers, P.A., Kumar, B., 2009, A sediment record of recent nutrient loading and trophic state change in Lake Norrviken, Sweden: Journal of Paleolimnology, v. 42, p. 325-341.

Routh, J., Meyers, P.A., Gustafsson, O., Baskaran, M., Hallberg, R., Scholdstro¨m, A., 2004, Sedimentary geochemical record of human induced environmental changes in the Lake Brunnsviken watershed, Sweden: Limnology and Oceanography, v. 49, p. 1560–1569.

Round, F.E., Crawford, R.M., and Mann, D.G., 1990, The Diatoms. Cambridge University Press, Cambridge. 469 p.

Roy, P.D., Caballero, M., Lozano, R., Ortega, B, Lozano, S, Pi, T., Israde, I., and Morton, O., 2010, Geochemical record of Late Quaternary paleoclimate from lacustrine sediments of paleo-lake San Felipe, western Sonora Desert, Mexico: Journal of South American

230

Earth Sciences, v. 29 p. 586–596.

Sandgren, P., Risberg, J., and, Thomsen, R., 1990, Magnetic susceptibility in sediment records of Lake Adran, eastern Sweden: correlation among cores and interpretation: Journal of Paleolimnology, v. 3, p.129-141.

Shawabkeh, K.H., 1998, The geology of Ma’in area. Map sheet no. 3153, 3. Bulletin 40. Amman: Geology Directorate, Geological map Division.

Sahawneh, J., 1996, Geology of Al Azraq Basin, Geology Directorate, Subsurface Geology Division, Groundwater Basin Project. Internal Report No. 2, Natural Resources Authority. Amman, Jordan.

Salameh, E., and Bannayan, H., 1993, Water Resources of Jordan present status and future potential. Published by Friedrich Edbert Stifung, Amman.

Sandgren, P., Risberg, J., and Thomsen, R., 1990, Magnetic susceptibility in sediment records of Lake Adran, eastern Sweden: correlation among cores and interpretation: Journal of Paleolimnology v. 3 , p. 129-141.

Schelske, C.L., and Hodell, D.A., 1991, Recent changes in productivity and climate of Lake Ontario detected by isotopic analysis of sediments: Limnology and Oceanography, v. 36, p. 961–975.

Schlesinger, W., 1996, Biogeochemistry: An Anylysis of Global Change. Second Edition. Academic Press. 588 p.

Schumacher, B., 2002, Methods for the determination of Total Organic Carbon (TOC) in soils and sediments: Ecological Risk Assessment Support Center, Office of Research and Development, Las Vegas, US Environmental Protection Agency.

Schwalb, A., Burns, S.J., and Kelts, K., 1999, Holocene environments from stable isotope stratigraphy of ostracodes and authigenic carbonate in Chilean Altiplano lakes: Palaeogeography, Palaeoclimatology, and Palaeoecology, v. 148, p. 153–168.

Schwalb, A., and Dean, W.E., 2002, Reconstruction of hydrological changes and response to effective moisture variations from North-Central USA lake sediments: Quarternary Science Reviews, v. 21, p. 1541-1554.

Scoffin, T.P., 1987, An Introduction to Carbonate Sediments and Rocks. Blackie, New York. 725 p.

Seppa, H., Hammarlund, D., and Antonsson, K., 2005, Low-frequency and high-frequency changes in temperature and effective humidity during the Holocene in south-central Sweden implications for atmospheric and oceanic forcings of climate: Climate

231

Dynamics, v. 25, p. 285-297.

Shahbaz, M., and Sunna, B., 2000, lntegrated Studies of the Azraq Basin in Jordan. USDA Forest Service Proceedings RMRS-P-13.

Shakkour, O., Rabb, I., and Sadeq, A., 2006, Feldspar. Geological Survey Adminstration. Mineral Status and Future Opportunity. Natural Resources Authority (NRA).

Sharma, S., Mora, G., Johnston, J.W., and Thompson T.A., 2005, Stable isotope ratios in swale sequences of Lake Superioras indicators of climate and lake level fluctuations during the Late Holocene: Quaternary Science Reviews, v. 24, p. 1941–1951.

Sharp, Z., 2007, Principles of Stable Isotope Geochemistry.Upper Saddle River, NJ, Pearson Education. 344 p.

Siegenthaler, U., and Eicher, U., 1986, Stable oxygen and carbon isotope analyses. In: Berglund, B.E. (Ed.), Handbook of Holocene Palaeoecology and Palaeohydrology. John Wiley and Sons Ltd, p. 407–422.

Sikes, N., and Ashley, G., 2007, Stable isotopes of pedogenic carbonates as indicators of paleoecology in the Plio-Pleistocene (upper Bed I), western margin of the Olduvai Basin, Tanzania: Journal of Human Evolution, v. 53, p. 574-594.

Sperber, C.M., Wilkinson, B.H., Peacor, D.R., 1984. Rock composition, dolomite stoichiometry, and rock/water reactions in dolomitic carbonate rocks. Journal of Geology, v. 92, p. 609–622.

Stein, R., 1990, Organic carbon content/sedimentation rate relationship and its paleoenvironmental significance for marine sediments: Geo-Marine Letters, v. 10, p. 37-44.

Stein, M., Torfstein, A., Gavrieli, I., Yechieli, Y., 2010, Abrupt aridities and salt deposition in the post-glacial Dead Sea and their North Atlantic connection: Quaternary Science Reviews, v. 29, p. 567–575.

Stoffers, P., and Botz, R., 1994, Formation of hydrothermal carbonate carbonate in lake Tanganyoka, East central Africa: Chemical Geology, v. 115, p. 117-122.

Stone, J., 2004, Three-dimensional modeling of lacustrine diatom habitat areas: Improving paleolimnological interpretation of planktic: benthic ratios. Limnology Oceanography, v. 49, p. 1540-1548.

Street-Perrott, A.F. and Perrott, A.R., 1990, Abrupt climate fluctuations in the tropics: the influence of Atlantic Ocean circulation: Nature, v. 343, p. 607–612.

232

Steinitz, G., and Bartov, Y., 1992, The Miocene-Pleistocene history of the Dead Sea segment of the rift in the light of K-Ar ages of basalt: Israel Journal of Earth Sciences, v. 40(1- 4), p. 199-208.

Stiller, M., 1977, Origin of sedimentation of components in Lake Kinneret traced by their isotopic composition. In: Interactions between sediments and freshwater. Proc. 1st Int. Symp. Junk. p.57-64.

Sun, X., Lu, H, Yi, S., and Jean-Jacques, B., 2013, Age and paleoenvironment of Paleolithic stone artifact remains discovered in the Tengger Desert, northern China: Journal of Arid Environment, v. 91, p. 129-137.

Talbot, M.R., 2001, Nitrogen isotopes in palaeolimnology. In: Tracking Environmenta Change Using Lake Sediments.Dordrecht, Kluwer Academic Publishers.

Talbot, M.R., 1990, A review of palaeohydrological interpretation of carbon and oxygen isotopic ratios in primary lacustrine carbonates: Chemical Geology (Isotope Geosciences Section), v. 80, p. 261–279.

Talbot, M.R., Jensen, N.B., Lardal, T., and Filippi, M.L., 2006, Geochemical responses to a major transgression in giant African lakes.: Journal of Paleolimnology, v. 35, p. 467- 489.

Talbot, M.R., and Johannessen, T., 1992, A high resolution paleoclimatic record for the last 27,500 years in tropical west Africa from the carbon and nitrogen isotopi composition of lacustrine organic matter. Earth and Planetary Science Letters, v. 110, p. 23-37.

Talbot, M.R. and Kelts, K.R., 1990, Paleolimnological signatures from carbon and oxygen stable isotopic ratios in carbonates from organic carbon-rich lacustrine sediments. In B. J. Katz & B. R. Rosendahl (ed.), Lacustrine Basin Exploration: Case Studies and Modern Analogues. Am. Assoc. Pet. Geol., p. 99-112.

Tarawneh, B., Yasin, S., Madanat, M., Mehyar, N., and Al-Omari,Y., 2006, Gypsum. Geological Survey Adminstration.Mineral Status and Future Opportunity. Natural Resources Authority (NRA), Amman Jordan.

Teranes, J.L., and Bernasconi, S.M., 2000, The record of nitrate utilization and productivity limitation provided by δ15N values in lake organic matter: a study of sediment trap and core sediments from Baldeggersee, Switzerland: Limnology and Oceanogr, v.45, p. 801–813.

Tenzer, G.E, Meyers, P.A., Ribbins, J.A., Eadie, B.J., Morehead, N.R., and Lansing, M.B., 1999, Sedimentary organic matter record of recent environmental changes in the St. Marys River ecosystem Michigan–Ontario border: Organic Geochemistry, v. 30, p, 133–146.

233

Thomsen, T., Finster, K., and Ramsing, N., 2001, Biogeochemical and Molecular Signatures of Anaerobic Methane Oxidation in a Marine Sediment: Applied Environment Microbiol: v. 67, p. 1646–1656.

Thompson, M., 1979, Magnetic Susceptiblity and particle-Size distribution in Recent Sediements of the Loch Lomond Drainge Basin, Scotland: Jornal of Sedimentary Petrology, v. 49, p. 0801-0812.

Thornton, S.F., and McManus, J., 1994, Application of organic carbon and nitrogen stable isotope and C/N ratios as sources indicator of organic matter provenance in estuarine system evidence from the Tay estuary, Scotland: Estuar Coast Shelf Science, v. 38, p. 219–233.

Torfstein, A., Haase-Schramm, Alexandra, Waldmann, Nicolas, Kolodny, Yehoshua, Stein, Mordechai, 2009, U-series and oxygen isotope chronology of the mid-Pleistocene Lake Amora (Dead Sea basin): Geochimica et Cosmochimica Acta, v. 73, p. 2603– 2630.

Turner, B., and Makhlouf, I., 2005, Quaternary sandstones, northeast Jordan: age, depositional environments and climatic implications: Palaeogeography, Palaeoclimatology, and Palaeoecology, v. 229, p. 230-250.

Turney, M., Beerling, D., Harkness, D., Lowe, J., and Scott, E., 1997, Stable carbon isotope variation in northwest Europe during the last glacial-interglacial transition.: Journal of Quaternary Science, v. 12, p. 339-344.

Tütken, T., Vennemann, T., Janz, H., and Heizmann, E., 2006, Palaeoenvironment and palaeoclimate of the Middle Miocene lake in the Steinheim basin, SW Germany: A reconstruction from C, O,andSr isotopes of fossil remains.: Palaeogeography, Palaeoclimatology, and Palaeoecology, v. 241, p. 457–491.

Tryon, R.C., 1939, Cluster Analysis. Ann Arbor, MI: Edwards Brothers.

Urey, H.C., 1948, Oxygen isotopes in nature and in the laboratory: Science, v. 108, p. 489- 496.

Valero-Garcés, B., Delgado-Huertas, A., Ratto, N., Navas, A., and Edwards, L., 2000, Paleohydrology of Andean saline lakes from sedimentological and isotopic records, Northwestern Argentina: Journal of Paleolimnology, v. 24, p. 343–359.

Valero-Garcés, L., Delgado-Huertas, A., Ratto, N., and Navas, A., 1999, Large 13C enrichment in primary carbonates from Andean altiplano lakes, northwest Argentina: Earth and Planetary Science Letters, v. 171, p. 253–266.

234

Van Rijn, L., 1993., Principles of Sediment Transport in Rivers, Estuaries, and Coastal Seas. Aqua Publications, Amsterdam.

Vassma, T., 2008., Grain-size analysis of lacustrine sediments: a comparison of pre- treatment methods: Estonian Journal of Ecology, v. 57, p. 231-245.

Verschuren, D., Laird, K.R., and Cumming, B.F., 2000, Rainfall and drought in equatorial east Africa during the past 1100 years: Nature, v. 403, p. 410–414.

Wang, Y., Deng, T., Flynn, L., Wang, X. , Yin, A., Yingfeng, X., Parker, W., Lochner, E., Zhang, C., and Biasatti, D., 2012, Late Neogene environmental changes in the central Himalaya related to tectonic uplift and orbital forcing: Journal of Asian Earth Sciences, v. 44, p. 62–76.

Watanabe, T., Naraoka, H., Nishimura, M., and Kawai, T., 2004, Biological and environmental changes in Lake Baikal during the late Quaternary inferred from carbon, nitrogen and sulfur isotopes: Earth and Planetary Science Letters, v. 222, p. 285-299.

Wolfe, B.B., Edwards T.W., and Aravena, R., 1999, Changes in carbon and nitrogen cycling duringtree-line retreat recorded in the isotopic content of lacustrine organic matter, western Taimyr Peninsula, Russia: Holocene, v. 9, p.215-222.

Wolin, J.A., and Duthie, H.C., 1999, Diatoms as indicators of water level change in freshwater lakes, pp. 183-202. In E. E. Stoermer and J. P. Smol [eds], The diatoms: Applications for the environmental and earth sciences. Cambridge Univ. Press.

Wood, W.W., 2000, Ground-water recharge in the Southern High Plains of Texas and New Mexico: U.S. Geological Survey Fact Sheet 127-99.

Woolfenden, W.B., and Ababneh, L., 2011, Late Holocene vegetation in the Azraq Wetland Reserve, Jordan: Quaternary Research, v. 76, p. 345-351.

Xu, H., Li A., Tan, L., and An, Z., 2006, Stable isotopes in bulk carbonates and organic matter in recent sediments of Lake Qinghai and their climatic implications: Chemical Geology, v. 235, p. 262–275.

Yager, T., 2000, The mineral industries of Jordan, Lebanon, and Syria. U.S geological survey minerals yearbook.

Yan, Z., and Petit-Maire, N., 1994, The last 140 ka in the Afro-Asian climatic transitional zone: Paleogeography, Paleoclimatology, Paleoecology, v. 110, p. 217–233.

Yu, J., 2005, Lake Qinghai, China: A multi-proxy investigation on sediment cores for the reconstructions of paleoclimate and paleoenvironment since the Marine Isotope

235

Stage 3. Dissertation. 127 p.

Yu, J.Q., Kelts, K.R., Chen, K.Z., Zhang, P.X., An, Z.S., 2000, An arid event at the Younger Dryas time window in the N. E. Tibet-Qinghai Plateau: Geolines. v. 11, p. 36-39.

Yasin, S., and Ghannam, A., 2006, Kaolinite.Geological SurveyAdministration. Mineral Status and Future Opportunity. Natural Resources Authority (NRA).

Zanchetta, G., Borghini, A., Fallick, A., and Bonadonna F.L., 2007, Late Quaternary palaeohydrology of Lake Pergusa (Sicily, southern Italy) as inferred by stable isotopes of lacustrine carbonates: Jounal of Paleolimnol, v. 38, p. 227–239.

Zhuo, Z., Baoyin, Y., and Petit-Maire, N., 1998, Paleoenvironments in China during the last glacial maximum and the Holocene optimum: Episodes, v. 21, p. 152–158.

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Vita

Khaldoun Ibrahim Ahmad was born in Iraq-Baghdad on April 26 1978. He studied in

Baghdad public schools and graduated from Al-Kendy High School in 1996. He attended the

University of Baghdad, Department of Geology in 1996. He graduated with a Bachelor of

Science degree in Geology in 2000. From 2002 to 2007 he worked for the University of

Baghdad Department of Geology as a lab assistant and instructor for geological courses:

General Geology, Optical Mineralogy, Ore Microscopy, and Field Methods.

Mr. Ahmad participated in the UMKC Department of Geoscience’s Jordan Paleolakes

Project before coming to the United States on September 19, 2007. In his first year he completed courses in English to qualify for graduate study. Mr. Ahmad then pursued a master’s degree in Organic Geochemistry at the University of Missouri-Kansas City,

Department of Geosciences which he completed in August 2010. Then he continued his education furthering a Ph.D. degree in Biogeochemistry and paleoenvironmental changes at the University of Missouri-Kansas City which he finished in May 2013.

Mr. Ahmad has received numerous academic scholarships during his studies. He received a full scholarship from the Iraqi Ministry of Higher Education to pursue his Organic

Geochemistry master’s degree in the United States. Then he received a teaching assistant scholarship from the department of Geosciences at the UMKC to complete the doctoral degree. During his studies at UMKC he received an Ambassador Scholarship for each semester from the University of Missouri-Kansas City.

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During his doctoral work at the university of Missouri-Kansas City, he taught an

Environmental Science lab, and developed a new course called an Introduction to

Biogeochemistry and was taught in spring 2013. Additionally, he advised undergraduate environmental science students.

Khaldoun Ahmad is a member of Geological Society of America, Geochemical

Society of America, Association of American Geography

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