Ellen E. Martin

Timing and Climatic Consequences of the Opening of Drake Passage

Age estimates for the opening of Drake Passage range from 49 to 17 million years ago (Ma), complicating interpretations of the relationship between ocean circulation and global cooling. Secular variations of neodymium isotope ratios at Agulhas Ridge (Southern Ocean, Atlantic sector) suggest an influx of shallow Pacific seawater approximately 41 Ma. The timing of this connection and the subsequent deepening of the passage coincide with increased biological productivity and abrupt climate reversals. Circulation/productivity linkages are proposed as a mechanism for declining atmospheric carbon dioxide. These results also indicate that Drake Passage opened before the Tasmanian Gateway, implying the late Eocene establishment of a complete circum-Antarctic pathway.

Preservation of seawater Sr and Nd isotopes in fossil fish teeth: bad news and good news ☆

Abstract We analyzed 87Sr/86Sr ratios in foraminifera, pore fluids, and fish teeth for samples ranging in age from Eocene to Pleistocene from four Ocean Drilling Program sites distributed around the globe: Site 1090 in the Cape Basin of the Southern Ocean, Site 757 on the Ninetyeast Ridge in the Indian Ocean, Site 807 on the Ontong-Java Plateau in the western equatorial Pacific, and Site 689 on the Maud Rise in the Southern Ocean. Sr isotopic ratios for dated foraminifera consistently plot on the global seawater Sr isotope curve. For Sites 1090, 757, and 807 Sr isotopic values of the pore fluids are generally less radiogenic than contemporaneous seawater values, as are values for fossil fish teeth. In contrast, pore fluid 87Sr/86Sr values at Site 689 are more radiogenic than contemporaneous seawater, and the corresponding fish teeth also record more radiogenic values. Thus, Sr isotopic values preserved in fossil fish teeth are consistently altered in the direction of the pore fluid values; furthermore, there is a correlation between the magnitude of the offset between the pore fluids and the seawater curve, and the associated offset between the fish teeth and the seawater curve. These data suggest that the hydroxyfluorapatite of the fossil fish teeth continues to recrystallize and exchange Sr with its surroundings during burial and diagenesis. Therefore, Sr chemostratigraphy can be used to determine rough ages for fossil fish teeth in these cores, but cannot be used to fine-tune age models. In contrast to the Sr isotopic system, our Nd concentration data, combined with published isotopic and rare earth element data, suggest that fish teeth acquire Nd during early diagenesis while they are still in direct contact with seawater. The concentrations of Nd acquired at this stage are extremely high relative to the concentrations in surrounding pore fluids. As a result, Nd isotopes are not altered during burial and later diagenesis. Therefore, fossil fish teeth from a variety of marine environments preserve a reliable and robust record of deep seawater Nd isotopic compositions from the time of deposition.

Fossil fish teeth as proxies for seawater Sr and Nd isotopes

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (site 807A, Ontong Java Plateau and site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater eNd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Eocene to Miocene magnetostratigraphy, biostratigraphy, and chemostratigraphy at ODP Site 1090 (sub-Antarctic South Atlantic)

At Ocean Drilling Program (ODP) Site 1090 (lat 42854.89S, long 8854.09E) located in a water depth of 3702 m on the Agulhas Ridge in the sub-Antarctic South Atlantic, ;300 m of middle Eocene to middle Miocene sediments were recovered with the advanced piston corer (APC) and the extended core barrel (XCB). U-channel samples from the 70‐230 meters composite depth (mcd) interval provide a magnetic polarity stratigraphy that is extended to 380 mcd by shipboard whole-core and discrete sample data. The magnetostratigraphy can be interpreted by the fit of the polarity-zone pattern to the geomagnetic polarity time scale (GPTS) augmented by isotope data and bioevents with documented correlation to the GPTS. Three normal-polarity subchrons (C5Dr.1n, C7Ar.1n, and C13r.1n), not included in the standard GPTS, are recorded at Site 1090. The base of the sampled section is correlated to C19n (middle Eocene), although the interpretation is unclear beyond C17r. The top of the sampled section is correlated to C5Cn (late early Miocene), although, in the uppermost 10 m

Nd isotopic excursion across Cretaceous ocean anoxic event 2 (Cenomanian-Turonian) in the tropical North Atlantic

Late Cretaceous fish debris from Demerara Rise exhibits a dramatic positive excursion of 8 ϵ Nd units during ocean anoxic event 2 (OAE2) that is superimposed on extremely low ϵ Nd(t) values (−14 to −16.5) observed throughout the rest of the studied interval. The OAE2 ϵ Nd excursion is the largest yet documented in marine sediments, and the majority of the shift is estimated to have occurred over Nd values on Demerara Rise are explained as the Nd isotopic signature of the South American craton, whereas eruptions of the Caribbean large igneous province or enhanced mixing of intermediate waters in the North Atlantic could have caused the excursion.

Consequences of shoaling of the Central American Seaway determined from modeling Nd isotopes

The Central American Seaway played a pivotal role in shaping global climate throughout the late Cenozoic. Recent geological surveys have provided new constraints on timing of the seaway shoaling, while neodymium isotopic (e Nd) data measured on fossil teeth, debris, and ferromanganese crusts have helped define the history of water masses in the region. Here we provide the first 3-D simulations of e Nd responses to the shoaling seaway. Our model suggests that a narrow and shallow seaway is sufficient to affect interoceanic circulation, that inflow/ outflow balance between the Caribbean and the Antilles responds nonlinearly to sill depth, and that a seaway narrower than 400 km is consistent with an active Atlantic meridional overturning circulation during the late Miocene. Simulated e Nd values in the Caribbean confirm that inputs from radiogenic Pacific waters in the Caribbean decrease as the seaway shoals. Despite model limitations, a comparison between our results and e Nd values recorded in the Caribbean helps constrain the depth of the Central American Seaway through time, and we infer that a depth between 50 and 200 m could have been reached 10 Ma ago.

Orbitally-Tuned Sr Isotope Chemostratigraphy for the Late Middle to Late Miocene

We present a Sr chemostratigraphic reference section for the late middle to late Miocene (14–5 Ma) from Ocean Drilling Program site 926 on the Ceara Rise. This site combines a precise, orbitally tuned timescale with a high sedimentation rate (15 m/m.y.), continuous deposition, and excellent biostratigraphic control. The Sr isotope curve is based on measurements of cleaned, planktonic foraminifera at 100–200 kyr sample intervals and it illustrates periods of rapid change in 87Sr/86Sr alternating with periods of little change. Chemostratigraphically-defined ages for these intervals can be determined within +/−0.8 m.y. and +/−1.6 m.y. respectively. There is excellent correlation with the published curve for site 588 [Hodell and Woodruff, 1994]; however the curve for site 747 [Oslick et al., 1994] exhibits less structure, which may be due to small errors in age estimates related to slow sedimentation rates, high-latitude fauna and an interval of complicated magnetics. Late Miocene data compare favorably with data from site 758 [Farrell et al., 1995].

Nutrient trap for Late Cretaceous organic-rich black shales in the tropical North Atlantic

Neodymium isotopes of fish debris from two sites on Demerara Rise, spanning ∼4.5 m.y. of deposition from the early Cenomanian to just before ocean anoxic event 2 (OAE2) (Cenomanian-Turonian transition), suggest a circulation-controlled nutrient trap in intermediate waters of the western tropical North Atlantic that could explain continuous deposition of organic-rich black shales for as many as ∼15 m.y. (Cenomanian–early Santonian). Unusually low Nd isotopic data (e Nd(t) ∼−11 to ∼−16) on Demerara Rise during the Cenomanian are confirmed, but the shallower site generally exhibits higher and more variable values. A scenario in which southwest-flowing Tethyan and/or North Atlantic waters overrode warm, saline Demerara bottom water explains the isotopic differences between sites and could create a dynamic nutrient trap controlled by circulation patterns in the absence of topographic barriers. Nutrient trapping, in turn, would explain the ∼15 m.y. deposition of black shales through positive feedbacks between low oxygen and nutrient-rich bottom waters, efficient phosphate recycling, transport of nutrients to the surface, high productivity, and organic carbon export to the seafloor. This nutrient trap and the correlation seen previously between high Nd and organic carbon isotopic values during OAE2 on Demerara Rise suggest that physical oceanographic changes could be components of OAE2, one of the largest perturbations to the global carbon cycle in the past 150 m.y.

Strontium and neodymium isotopic analyses of marine barite separates

Strontium and neodymium isotopic data are reported for barite samples chemically separated from Late Miocene to Pliocene sediments from the eastern equatorial Pacific. At a site within a region of very high productivity close to the equator, 875r/86Sr ratios in the barite separates are indistinguishable from those of foraminifera and fish teeth from the same samples. However, at two sites north of the productivity maximum barite separates have slightly, but consistently lower (averaging 62 × 10 -6) ratios than the coexisting phases, although values still fall within the total range of published values for the contemporaneous seawater strontium isotope curve. We examine possible causes for this offset including recrystallization of the foraminifera, fish teeth or barite, the presence of non-barite contaminants, or incor- poration of older, reworked deep-sea barite; the inclusion of a small amount of hydrothermal barite in the sediments seems most consistent with our data, although there are difficulties associated with adequate production and transportation of this phase. Barite is unlikely to replace calcite as a preferred tracer of seawater strontium isotopes in carbonate-rich sediments, but may prove a useful substitute in cases where calcite is rare or strongly affected by diagenesis. In contrast to the case for strontium, neodymium isotopic ratios in the barite separates are far from expected values for contemporary seawater, and appear to be dominated by an (unobserved) eolian component with high neodymium concentration and low 143Nd( ~44Nd. These results suggest that the true potential of barite as an indicator of paleocean neodymium isotopic ratios and REE patterns will be realized only when a more selective separation procedure is developed.

Circulation through the Central American Seaway during the Miocene carbonate crash

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 ϵNd 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 ϵNd 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 ϵNd 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 ϵNd values following the carbonate crash.