Nd isotopic composition of fossil fish teeth and debris from ODP Legs 138, 165, and 202

Changes in circulation associated with the shoaling of the Isthmus of Panama and the Caribbean carbonate crash in the Miocene were investigated using Nd isotopes from fossil fish teeth and debris from two sites in the Caribbean Basin (Ocean Drilling Program Sites 998 and 999) and two sites in the eastern equatorial Pacific (Sites 846 and 1241). The total range for e-Nd values measured from 18 to 4.5 Ma in the Caribbean is -7.3 to 0. These values are higher than Atlantic water masses (~-11) and range up to values equivalent to contemporaneous Pacific water masses, confirming that flow into the Caribbean Basin was composed of a mixture of Pacific and Atlantic waters, with an upper limit of almost pure Pacific-sourced waters. Throughout the Caribbean record, particularly during the carbonate crash (10-12 Ma), low carbonate mass accumulation rates (MARs) correlate with more radiogenic e-Nd values, indicating increased flow of corrosive Pacific intermediate water into the Caribbean Basin during intervals of dissolution. This flow pattern agrees with results from general ocean circulation models designed to study the effect of the shoaling of the Central American Seaway. Low carbonate MARs and high e-Nd values also correlate with intervals of increased Northern Component Water production and, therefore, enhanced conveyor circulation, suggesting that the conveyor may respond to changes in circulation associated with shoaling of the Central American Seaway. Reduced Pacific throughflow related to shoaling of the seaway led to a gradual increase in carbonate preservation and more Atlantic-like e-Nd values following the carbonate crash.

Calcium carbonate contents and carbon and oxygen isotope compositions of bulk carbonate, ODP Leg 165 sediments

Two recently drilled Caribbean sites contain expanded sedimentary records of the late Paleocene thermal maximum, a dramatic global warming event that occurred at ca. 55 Ma. The records document significant environmental changes, including deep-water oxygen deficiency and a mass extinction of deep-sea fauna, intertwined with evidence for a major episode of explosive volcanism. We postulate that this volcanism initiated a reordering of ocean circulation that resulted in rapid global warming and dramatic changes in the Earth's environment.

Susceptibility, density, iron and calcium concentrations of ODP holes 165-999B and 165-1001A

Pelagic sediments recording an extreme and short-lived global warming event, the Late Paleocene Thermal Maximum (LPTM), were recovered from Hole 999B (Colombian Basin) and Holes 1001A and 1001B (lower Nicaraguan Rise) in the Caribbean Sea during Ocean Drilling Program Leg 165. The LPTM consists of a 0.3-0.97 m calcareous claystone to claystone horizon. High-resolution downhole logging (Formation MicroScanner [FMS]), standard downhole logs (resistivity, velocity, density, natural gamma ray, and geochemical log), and non-destructive chemical and physical property (multisensor core logger [MSCL] and X-ray fluorescence [XRF] core scanner) data were used to identify composite sections from parallel holes and to record sedimentological and environmental changes associated with the LPTM. Downhole logging data indicate an abrupt and distinct difference in physical and chemical properties that extend for tens of meters above and below the LPTM. These observations indicate a rapid environmental change at the LPTM, which persists beyond the LPTM anomaly. Comparisons of gamma-ray attenuation porosity evaluator (GRAPE) densities from MSCL logging on split cores with FMS resistivity values allows core-to-log correlation with a high degree of accuracy. High-resolution magnetic susceptibility measurements of the cores are compared with elemental concentrations (e.g., Fe, Ca) analyzed by high-resolution XRF scanning. The high-resolution data obtained from several detailed core and downhole logging methods are the key to the construction of composite sections, the correlation of both adjacent holes and distant sites, and core-log integration. These continuous-depth series reveal the LPTM as a multiphase event with a nearly instantaneous onset, followed by a much different set of physical and chemical conditions of short duration, succeeded by a longer transition to a new, more permanent set of environmental circumstances. The estimated duration of these 'phases' are consistent with paleontological and isotopic studies of the LPTM

Range charts of stratigraphically important radiolarian species in sediments of ODP Leg 165 sites

The Paleogene sequences from three sites in the Caribbean were examined for radiolarians. In general, samples are highly lithified, requiring lengthy and repetitive cleaning procedures, and the assemblages are usually fragmented and/or partially dissolved. Both abundances and preservation of the assemblages vary considerably from site to site and within a single site; even within a single sample more than one degree of preservation was observed. It was possible, however, to construct at least partial stratigraphies for each of the three sites. Because the abundance of radiolarians is high even in extremely poorly preserved assemblages, we conclude that the differences in biogenic silica preservation are the result of postdepositional processes and not productivity. In both Sites 999 and 1001, near the Paleocene/Eocene boundary (Bekoma bidartensis Zone [RP7]), there is a short interval in which the abundance and preservation state of the radiolarians improves relative to overlying and underlying assemblages. In each case the intervals corresponds to the level, identified by calcareous microfossils, as representing changes in paleoceanographic conditions associated with the late Paleocene thermal maximum.

Oxygen isotopes and hydrocarbon composition of gas hydrate and hydrate water from ODP Leg 165 sites

Ocean Drilling Program (ODP) Leg 164 recovered a number of large solid gas hydrate from Sites 994, 996, and 997 on the Blake Ridge. Sites 994 and 997 samples, either nodular or thick massive pieces, were subjected to laboratory analysis and measurements to determine the structure, molecular and isotopic composition, thermal conductivity, and equilibrium dissociation conditions. X-ray computed tomography (CT) imagery, X-ray diffraction, nuclear magnetic resonance (NMR), and Raman spectroscopy have revealed that the gas hydrates recovered from the Blake Ridge are nearly 100% methane gas hydrate of Structure I, cubic with a lattice constant of a = 11.95 ± 0.05 angström, and a molar ratio of water to gas (hydration number) of 6.2. The d18O of water is 2.67 per mil to 3.51 per mil SMOW, which is 3.5-4.0 heavier than the ambient interstitial waters. The d13C and dD of methane are -66 per mil to -70 per mil and -201 per mil to -206 per mil, respectively, suggesting that the methane was generated through bacterial CO2 reduction. Thermal conductivity values of the Blake Ridge hydrates range from 0.3 to 0.5 W/(m K). Equilibrium dissociation experiments indicate that the three-phase equilibrium for the specimen is 3.27 MPa at 274.7 K. This is almost identical to that of synthetic pure methane hydrate in freshwater.

Benthic foraminifera accumulation rate and benthic foraminiferal productivity proxies at ODP Site 165-999 in the Caribbean (Appendix A)

This study tests the hypothesis that the late Miocene to early Pliocene constriction and closure of the Central American Seaway (CAS), connecting the tropical Atlantic and East quatorial Pacific (EEP), caused a decrease in productivity in the Caribbean, due to decreased coastal upwelling and an end to the connection with high-productivity tropical Pacific waters. The present study compared paleoceanographic proxies for the interval between 8.3 and 2.5 Ma in 47 samples from south Caribbean ODP Site 999 with published data on EEP DSDP Site 503. Proxies for Site 999 include the relative abundance of benthic foraminiferal species representing bottom current velocity and the flux of organic matter to the sea floor, the ratio of infaunal/epifaunal benthic foraminiferal species and benthic foraminifer accumulation rates (BFARs). In addition, we calculated % resistant planktic foraminifers species and used the previously published % sand fraction and benthic carbon isotope values from Site 999. During early shoaling of the Isthmus (8.3-7.9 Ma) the Caribbean was under mesotrophic conditions, with little ventilation of bottom waters and low current velocity. The pre-closure interval (7.6-4.2 Ma) saw enhanced seasonal input of phytodetritus with even more reduced ventilation, and enhanced dissolution between 6.8 and 4.8 Ma. During the post-closure interval (4.2-2.5 Ma) in the Caribbean, paleoproductivity decreased, current velocity was reduced, and ventilation improved, while the seasonality of phytodetrital input was reduced dramatically, coinciding with the establishment of the Atlantic-Pacific salinity contrast at 4.2 Ma. Our data support the hypothesis that late Miocene constriction of the CAS at 7.9 Ma and its closure at 4.2 Ma caused a gradual decrease in paleoproductivity in the Caribbean, consistent with decreased current velocity and seasonality of the phytodetrital input.