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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 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 ii 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. iii 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 iv 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 v 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 vi 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
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