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Hydrology, source region, and timing of precipitation are important controls on the climate of the Great Plains of North America and the composition of terrestrial ecosystems. Moisture delivered to the Great Plains varies seasonally and predominately derives from the Gulf of Mexico/Atlantic Ocean with minor contributions from the Pacific Ocean and Arctic region. For this work, we evaluate long-term relationships for the past ~ 35 million years between North American hydrology, climate, and floral change, using isotopic records and average carbon chain lengths of higher plant n-alkanes from Gulf of Mexico sediments (DSDP Site 94). We find that carbon isotope values (d13C) of n-alkanes, corrected for variations in the d13C value of atmospheric CO2, provide minor evidence for contributions of C4 plants prior to the Middle Miocene. A sharp spike in C4 input is identified during the Middle Miocene Climatic Optimum, and the influence of C4 plants steadily increased during the Late Miocene into the Pleistocene - consistent with other North American records. Chain-length distributions of n-alkanes, indicative of the composition of higher plant communities, remained remarkably constant from 33 to 4 Ma. However, a trend toward longer chain lengths occurred during the past 4 million years, concurrent with an increase in d13C values, indicating increased C4 plant influence and potentially aridity. The hydrogen isotope values (dD) of n-alkanes are relatively invariant between 33 and 9 Ma, and then become substantially more negative (75 per mil) from 9 to 2 Ma. Changes in the plant community and temperature of precipitation can solely account for the observed variations in dD from 33 to 5 Ma, but cannot account for Plio-Pleistocene dD variations and imply substantial changes in the source region of precipitation and seasonality of moisture delivery. We posit that hydrological changes were linked to tectonic and oceanographic processes including the shoaling and closure of the Panamanian Seaway, amplification of North Atlantic Deep Water Production and an associated increase of meridional winds. The southerly movement of the Intertropical Convergence Zone near 4 Ma allowed for the development of a near-modern pressure/storm track system, driving increased aridity and changes in seasonality within the North American interior.

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The Quaternary history of metastable CaCO3 input and preservation within Antarctic Intermediate Water (AAIW) was examined by studying sediments from ODP Holes 818B (745 mbsl) and 817A (1015 mbsl) drilled in the Townsville Trough on the southern slope of the Queensland Plateau. These sites lie within the core of modern AAIW, and near the aragonite saturation depth (~1000 m). Thus, they are well positioned to monitor chemical changes that may have occurred within this watermass during the past 1.6 m.y. The percent of fine aragonite content, percent of fine magnesian calcite content, and percent of whole pteropods (>355 µm) were used to separate the fine aragonite input signal from the CaCO3 preservation signal. Stable d18O and d13C isotopic ratios were determined for the planktonic foraminifer Globigerinoides sacculifer and, in Hole 818B, for the benthic foraminifer Cibicidoides spp. to establish the oxygen isotope stratigraphy and to study the relationship between intermediate and shallow water d13C of Sum CO2 and the relationship between benthic foraminiferal d13C and CaCO3 preservation within intermediate waters of the Townsville Trough. Data were converted from depth to age using oxygen isotope stratigraphy, nannostratigraphy, and foraminiferal biostratigraphy. Several long hiatuses and the absence of magnetostratigraphy did not permit time series analysis. The principal results of the CaCO3 preservation study include the following (1) a general increase in CaCO3 preservation between 0.9 and 1.6 Ma; (2) a CaCO3 dissolution maximum near 0.9 Ma, primarily expressed in the Hole 818B fine aragonite record; (3) an abrupt and permanent increase of fine aragonite content between 0.86 and 0.875 Ma in both Holes 818B and 817A probably reflecting a dramatic increase of fine carbonate sediment production on the Queensland Plateau; (4) an improvement in CaCO3 preservation near 0.87 Ma, which accompanied the increase of sediment input, indicated by the first appearance of whole pteropods in the deeper Hole 817A and a "spike" in the percent whole pteropods in Hole 818B; (5) a period of strong CaCO3 dissolution during the mid-Brunhes Chron from 0.36 to 0.41 Ma; and (6) a complex CaCO3 preservation pattern between 0.36 Ma and the present characterized by a general increase in CaCO3 preservation through time with good preservation during interglacial stages and poor preservation during glacial stages. The long-term aragonite preservation histories for Holes 818B and 817A appear to be similar in general shape, although different in detail, to CaCO3 preservation records from the deep Indian and central equatorial Pacific oceans as well as from intermediate water sites in the Bahamas and the Maldives. All of these areas have experienced CaCO3 dissolution at about 0.9 Ma and during the mid-Brunhes Chron. However, the late Quaternary (0 to 0.36 Ma) glacial to interglacial preservation pattern in Holes 818B and 817A is out of phase with CaCO3 preservation records for sediments deposited in Pacific deep and bottom waters. The sharp increase in bank production and export from the Queensland Plateau and the coincident improvement of CaCO3 preservation between 0.86 and 0.875 Ma may have been synchronous with the initiation of the Great Barrier Reef and roughly coincides with an increase in carbonate accumulation on the Bahama banks, in the western North Atlantic Ocean, and on Mururoa atoll, in the central South Pacific Ocean. The development of these reef systems during the middle Quaternary may be related to the transition in the frequency and amplitude of global sea level change from 41 k.y. low amplitude cycles prior to 0.9 Ma to 100 k.y. high amplitude cycles after 0.73 Ma. Carbon isotopic analyses show that benthic foraminiferal d13C values (Cibicidoides spp.) have been heavier than planktonic foraminiferal d13C values (G. sacculifer) throughout most of the last 0.54 m.y., which may indicate that 13C-enriched intermediate water (AAIW) occupied the Townsville Trough during much of the late Quaternary. Furthermore, both planktonic and benthic foraminiferal d13C values are often observed to be heaviest during interglacial to glacial transitions, and lightest during glacial to interglacial transitions. We suggest that this pattern is the result of changes in the preformed d13C of Sum CO2 of AAIW and may reflect changes in nutrient utilization by primary producers in Antarctic surface waters, changes in the d13C of upwelled Circumpolar Deep Water, or changes in the extent and/or temperature of equilibration between surface water and atmospheric CO2 within the Antarctic Polar Frontal Zone (the source area for AAIW). Finally, the poor correlation between percent of whole pteropods (aragonite preservation) and d13C of Cibicidoides spp. may be the result of a decoupling of d13C from CO2 due to the numerous and complex variables that combine to produce the preformed d13C of AAIW.