Warm Saline Deep Water Production in the Eocene-Early Oligocene

Warm Saline Deep Water Production in the middle Eocene-early Oligocene

PI: Ellen E. Martin, University of Florida

Funded by: American Chemical Society, Petroleum Research Fund, 2005

1 Abstract The goal of this proposal is to use Nd isotopes preserved in fossil fish teeth and authigenic Fe-Mn oxide coatings on sediment to test the idea that warm saline deep waters (WSDW) produced at low latitudes filled much of the deep ocean during intervals in the middle Eocene through early Oligocene. The existence of WSDW has dramatic implications for poleward heat transport, nutrient distributions and the preservation of organic carbon; however, previous studies based on other proxies, such as stable isotopes and sedimentary parameters, yield equivocal results. Nd isotopes preserved in deep marine archives are considered “quasi-conservative” tracers of water mass because the primary signature imparted in the source region of a particular water mass is predominantly altered by mixing of water mass, but can also be affected by local continental inputs. This study will apply a multi-proxy approach; the Nd isotopic records will be compared to: 1) records of Pb isotopes from the coatings also collected during this study, 2) published stable isotope records from benthic foraminifera, 3) published clay mineralogy records, and 4) published sedimentary parameters, in order to isolate the component of the Nd isotopic record that correlates to circulation. Records of these proxies from 3 Ocean Drilling Program (ODP) sites in the Southern Ocean (sites 689, 690, and 699) will be used to test the theory that WSDW was an important component of deep ocean circulation during the middle Eocene through early Oligocene and that it contributed to the warm, equitable climate.

Project Description Introduction to the Problem The Eocene to Oligocene interval marks a critical time in the evolution of deep ocean circulation patterns and the transition from a greenhouse to an icehouse world. For much of the Cenozoic deep and bottom waters appear to have formed at high latitudes, as they do today, resulting in deep ocean waters that are relatively cold and moderately salty. Chamberlin (1906) suggested that these cold, dense bottom waters could have been replaced by warm, salty deep waters formed at low latitudes when the polar regions were relatively warm and ice-free, and the pole to equator temperature gradient was low, as in the Eocene. Kennett and Stott (1990) named the ocean typified by this reversed form of meridional overturn the “Proteus Ocean,” (Fig. 1) and argued that it represented the dominant circulation pattern for most of the Eocene based on evidence from ODP sites 689 and 690. The goal of this proposal is to test the theory that warm saline deep water (WSDW) formed during the middle Eocene through early Oligocene (~28-44 Ma) using Nd isotopes, a relatively new tracer for water mass.

2 Fig. 1 The Proto-oceanus and Proteus ocean circulation patterns for the Atlantic proposed by Kennett and Stott (1990). For Oligocene and Eocene times warm, salty water from high latitude sources is common in the Southern Ocean. AAIW = Antarctic Intermediate Water; AABW = Antarctic Bottom Water. From Kennett and Stott (1990).

Determining the mode of ocean circulation in the past is critical for understanding the role circulation plays in driving global climate change. Formation of WSDW has major implications for poleward heat transport, nutrient distributions and preservation of organic matter. Although the Proteus Ocean model represents a fundamentally different mode of ocean circulation than the system that prevailed for most of the Cenozoic; 1) general circulation models (GCMs) (Barron, 1987; Rind and Chandler, 1991; Barron and Peterson, 1992; Sloan et al., 1995, Bice et al., 1997 and 1998; Bice and Marotzke, 2001), 2) stable isotopic studies (Kennett and Stott, 1990 and 1991; Mackenson and Ehrmann, 1992; Mead and Hodell, 1992; Pak and Miller, 1992; Zachos et al., 1992; Wright and Miller, 1993), and 3) studies of a variety of sedimentary parameters, such as carbonate preservation (Diester-Haass et al., 1993 and 1996; Diester-Haass, 1995; Diester-Haass and Zahn, 1996), sediment composition (Oberhänsli and Hsü, 1986; Ehrmann and Mackensen, 1992), and CCD fluctuations (Oberhänsli and Hsü, 1986), have not been able to resolve whether or not there were significant intervals of WSDW production. This is because of the limitations imposed on GCMs by our knowledge of boundary conditions and because stable isotopes, carbonate preservation, and sediment composition are not conservative tracers of water mass.

3 The research plan for this proposal is to analyze Nd and Pb isotopic compositions of Fe- Mn oxide coatings and fish teeth from three sites in the Atlantic sector of the Southern Ocean in order to evaluate the existence and extent of WSDW formation during the middle Eocene through early Oligocene. The Nd isotopic signal records a combination of deepwater circulation plus weathering inputs. This project will use a multiproxy approach to deconvolve these aspects of the Nd record. The circulation component of this signal will be isolated by comparison to stable isotopes and sedimentary properties related to water mass, while the weathering component will be identified by correlation to Pb isotopes plus pre-existing data on clay mineralogy. This study will focus on sites 689, 690 and 699 in the Southern Ocean because there should be a clear distinction between younger, cooler, nutrient-rich southern component deep waters with Nd values between

-6 and -9 and older, warmer, nutrient-poor WSDW with Nd values less than –9.5 (Nd represents deviations in parts per 104 of the 143Nd/144Nd ratio relative to the chondritic uniform reservoir; Jacobsen and Wasserburg, 1980).

Scientific Significance WSDW production associated with the Proteus Ocean model may impact climate through: 1) poleward heat transport, 2) nutrient and productivity distributions, and 3) hydrocarbon generation via organic carbon preservation. Some GCM’s for the Paleogene indicate it is impossible to generate the documented low pole-to-equator thermal gradient and ice-free conditions without increased poleward heat transport, which could be accomplished through WSDW circulation (Barron, 1987; Rind and Chandler, 1991; Barron and Peterson, 1992; Sloan et al., 1995). However, newer models with more realistic seafloor bathymetry and continental runoff calculations indicate that it may be difficult to generate WSDW in the Tethys region (Bice et al., 1998; Bice et al., 1997; Bice and Marotzke, 2001) and Sloan et al. (1995) argued that extreme quantities of WSDW would be required to generate sufficient poleward heat transport to sustain Eocene conditions. Ultimately, the test of WSDW production and the Proteus Ocean model will depend on data that can identify changes in water mass and ocean circulation patterns.

4 A low latitude source of deep water would affect the distribution of nutrients in the ocean. In high-nutrient, low-chlorophyll regions of the high latitude oceans (Chisholm and Morel, 1991) surface nutrients are not fully utilized by biological productivity due to limitations imposed by temperature, light and possibly iron availability (Martin and Fitzwater, 1988). As a result, significant concentrations of nutrients are carried into the deep ocean as “preformed” nutrients, representing a key inefficiency in the conversion of dissolved nutrients to organic matter. In contrast, phytoplankton tend to extract nutrients more efficiently in low latitude surface waters; thus, convecting waters in low latitude source regions carry a greater load of organic matter into the deep ocean. Herbert and Sarmiento (1991) pointed out that this load, combined with the lower saturation of oxygen in warmer downwelling waters (Brass et al., 1982), could lead to deep water anoxia on a large scale. Although deep sea records of bioturbation argue against such periods of extensive anoxia, the model by Herbert and Sarmiento (1991) illustrates that changes in deep sea circulation patterns could effect organic carbon preservation. Typically >99% of the organic carbon rain is recycled before deep burial. In contrast, periods of WSDW formation could be associated with enhanced organic carbon preservation and deposition of potential hydrocarbon source rocks.

Background Evidence for WSDW Much of the evidence for the production of WSDW comes from studies of stable isotopes. Kennett and Stott (1990) interpreted the 18O data from sites 689 and 690 to indicate a temperature inversion with warmer waters underlying cooler waters (Fig. 2). Other authors have documented evidence for WSDW, but often for shorter intervals of time. In some studies the evidence supports smaller-scale, intermittent plumes of intermediate to upper deep water masses from a low latitude source (Mackensen and Ehrmann, 1992; Pak and Miller, 1992; Zachos et al., 1992; Wright and Miller, 1993), or mixing of a plume of WSDW with high latitude source waters (Mead et al., 1993), rather than a true Proteus Ocean model with WSDW filling the deep ocean. Carbon isotopes are potential tracers of water mass age (Kroopnick, 1985) and, therefore, circulation patterns. However, interpretations of 13C data from the Eocene to Oligocene

5 Fig. 2 18O data from Kennett and Stott (1990) vs. age for ODP sites 689 and 690. The ages have been converted to Cande and Kent (1995) and corrected using Sr chemostratigraphy. Intervals with lower 18O values in site 690 relative to site 689 indicate times when waters bathing the deeper site (690) may have been warmer than those bathing the shallower site (689).

are complicated by a very small 13C gradient throughout the ocean basins, which may indicate one dominant source region with rapid ventilation (Wright and Miller, 1993), oligotrophic surface conditions, or multiple deep water sources (Mead et al., 1993). Based on 13C studies Wright and Miller (1993) argued that the Southern Ocean was the dominant source of deep water from the late Eocene to Miocene. In contrast, Zachos et al., (1992) found evidence for a Tethyan-Indian Saline Water mass at intermediate to deep water sites in the Indian Ocean, and Pak and Miller (1992) cite evidence for possible WSDW in the North Atlantic and Pacific.

Interpretations of stable isotope records are complicated by the fact that 18O is not a pure tracer of temperature and 13C is not a true tracer for water mass. Although studies of 18O from several sites support the presence of a warmer deep water mass (Fig. 2), 18O is influenced by both the isotopic composition of seawater (reflecting ice volume and salinity) and the temperature. Ice volume is more difficult to estimate for the Oligocene, but the Eocene is generally assumed to be ice-free. The two remaining variables, temperature and salinity, are exactly the two water mass properties that change during WSDW formation. 13C interpretations are limited by the small gradient in the Eocene/Oligocene. In additional, 13C is affected by the rain rate of organic carbon,

6 mixing between water masses with different compositions, and variations in the carbonate ion concentration (Spero et al., 1997).

Diester-Haass and co-workers (Diester-Haass, 1995; Diester-Haass et al., 1996) identified intervals of WSDW production using estimates of surface productivity and carbonate preservation. They argued that intervals of high productivity coupled with high carbonate preservation indicated the presence of WSDW that would chemically favor carbonate preservation. In contrast, intervals with low productivity and high carbonate dissolution were interpreted to represent corrosive proto-AABW (Antarctic Bottom Water).

Nd Isotopes as Water Mass Tracers Nd isotopes are viewed as quasi-conservative tracers of water masses. The residence time of Nd in seawater (~1000 yrs; Elderfield and Greaves, 1982; Piepgras and Wasserburg, 1985; Jeandel et al., 1995; Tachikawa et al., 1999) is shorter than the mixing time of the oceans (~1500 yrs; Broecker and Peng, 1982), and Nd is predominantly sourced from the continents (see Frank, 2002). As a result, the cores of individual water masses have distinct Nd values that reflect continental weathering in their source regions (Piepgras and Wasserburg, 1982 and 1987; Piepgras and Jacobsen, 1988; Bertram and Elderfield, 1993; Jeandel, 1993; Shimizu et al., 1994; Jeandel et al., 1998). The “quasi- conservative” terminology reflects the fact that the initial signal imparted in the source region can be modified by weathering inputs during circulation; however, the isotopic distinction between many water masses is large enough that it is still possible to detect mixing and changes in circulation despite regional weathering effects (Piepgras and Jacobsen, 1988).

Pb Isotopes as tracers of Weathering Inputs Pb has a much shorter residence time in the ocean (~80-100 yrs), thus Pb isotopic studies illustrate regional variations that are attributed to changes in weathering inputs (e.g. Abouchami et al., 1997; Frank and O’Nions, 1998; Reyolds et al., 1999; Claude-Ivanaj et al., 2001; von Blanckenburg and Nägler, 2001; Abouchami et al., 2003; Frank et al.,

7 2003). von Blanckenburg and Nägler (2001) warned that Pb isotopic ratios in seawater may not exactly reflect source materials due to incongruent weathering; however, numerous studies have identified reasonable source components using Pb-Pb isotope crossplots.

Archives of Nd Isotopes Published studies of Nd and Pb isotopes as proxies for ocean circulation and weathering rely on Fe-Mn crusts as archives (e.g. Abouchami et al., 1997; Burton et al., 1997 and 1999; Ling et al., 1997; O’Nions et al., 1998; Frank et al., 1999; von Blanckenburg and O’Nions, 1999; Frank et al., 2002); however, these crusts have limited spatial and temporal distributions, are difficult to date, and accumulate extremely slowly, on the order of 1-10 mm/myr. This slow accumulation rate is problematic because it means the crusts tend to integrate the bottom water isotopic composition over long periods of time. Therefore, the isotopic records from crusts lack the resolution necessary for detailed studies of paleocean circulation.

Fossil fish teeth and authigenic Fe-Mn oxide coatings on sediment represent more ideal archives for Nd isotopes. Martin and Haley (2000) and Martin and Scher (2004) documented that fish teeth incorporate deep water Nd isotopes during early diagenesis and preserve that value during burial. As a result, fossil teeth can be used to construct high-resolution records of secular variations in Nd isotopes. The one disadvantage of fish teeth as an archive is that they are time consuming to pick and clean, and they are not always available in sufficient quantities.

Dispersed authigenic Fe-Mn oxide coatings on sediment particles represent an alternative archive for Nd isotopes. These coatings represent the same material that accumulates in Fe-Mn crusts, but in this case the oxides precipitate on the surface of sedimentary particles. The coatings are ubiquitous in marine sediments and they incorporate high concentrations of Nd along with Pb and other trace metals. Published records demonstrate that coatings on biogenic and detrital particles record high-resolution variations in NADW over Pleistocene glacial/interglacial cycles (Rutberg et al., 2000;

8 Bayon et al., 2002), and even millennial time scales (Piowtrowski et al., 2004). Palmer and Elderfield (1986) presented a low-resolution record of Nd isotopic data from coatings on uncleaned foraminifera for samples spanning the Cenozoic. Recent work at the University of Florida (UF) illustrates that coatings leached from the >63 m fraction of the sediment from two of the sites proposed for this study and site 1090 yield Nd isotopic values comparable to values preserved in fish teeth (Fig. 3) (Blair et al., 2004).

Fig. 3 a Nd(0) vs. age for a) site 1090, b) site 689, and c) site 690. Blue symbols illustrate the values for fish teeth, while red symbols represent values from Fe-Mn oxide coatings. For almost all sample pairs the values for the two different archives agree within error. Note different scales in each plot.

b 689 c 690

9 Work Plan The Nd isotopic record for site 689 has already been generated and submitted for publication (Scher and Martin, submitted). The plan for this proposal is to have a graduate student compile Nd and Pb isotope records for the middle Eocene through early Oligocene from ODP sites 690 and 699 and complete a Pb isotopic record for site 689 (Table 1, Fig.4). Derrick Newkirk is currently completing is first year of a MS program with a teaching assistantship. This proposal would support his research, stipend and tuition for the additional 1.5 years projected until his completion (summer ’05 through Fall ’06), as well as partial support for travel to one meeting (Fall AGU) each year for the PI and Derrick.

Fig. 4 Location map for sites to be studied for this project.

Site 699

Site 690 Site 689

Table 1. Location and information on the ODP sites proposed for this study.

Site/Leg Location Modern water Paleo depth Average sed. depth (m) (~40 Ma) Rate (m/m.y.) Site 689/1131 64°31’S, 3°06’E 2080 1438 3 5 4,5 Site 690/1131 65°09S, 1°12’E 2914 2240 3 3 5 Site 699/1142 51°32’S, 30°40’W 3705 3431 3 14 3 1 Site 689 and 690 location and water depth from Barker, Kennett et al. (1988a and b). 2 Site 690 location and water depth from Ciesielski, Kristoffersen et al. (1988). 3 Mead et al.(1993) 4 Spiess (1990) 5 Bohaty and Zachos (2003)

Site Information

10 Sites 689 and 690 located on Maud Rise were chosen because intervals of WSDW have been identified at these locations, particularly the deeper site 690 (Fig. 2). There are no sediments from the deep Tethys preserved in the ocean today; therefore, site 690 will also provide the framework for determining whether a unique water mass signature is

associated with intervals of purported WSDW, and it will be used to define the Nd value of that water mass. Site 699 is included because it is a deeper site and will test whether the WDSW occurred as a true deep water mass or a plume at intermediate depths. Age models for all 3 sites will be established by adjusting biostratigraphic datums (Table 2) to the time scale by Berggren et al. (1995), and magnetostratigraphic data (Table 2) to the time scales of Cande and Kent (1995). Sr chemostratigraphy for the late Eocene to early Oligocene will be applied as needed; however, the Sr curve is too flat in the middle Eocene to allow accurate age determinations.

Table 2. Supplementary data for sites for this study. Site Stable Clay Additional Biostrat Magnetostrat Isotope Mineralogy Sedimentary Datums Datums Data Parameters 689 1, 2, 3, 4 2, 6, 7, 8 2, 3, 8 9 12, 13, 14 17 690 1, 2 2, 6 2, 10 12, 13, 14 17 699 5 11 13, 15, 16 18 1 Kennett and Stott (1990 and 1991) 2 Mackensen and Ehrmann (1992) 3 Diester-Haass and Zahn (1996) 4 Bohaty and Zachos (2003) 5 Mead et al. (1993) 6 Ehrmann and Mackensen, 1992 7 Robert and Kennett (1997) 8 Robert et al. (2002) 9 Barker and Kennett et al (1988a) 10 Barker and Kennett et al. (1988b) 11 Ciesielski and Kristoffersen et al. (1988) 12 Stott and Kennett (1990) 13 Wei (1992) 14 Wei and Wise (1990) 15 Madile and Monechi (1991) 16 Wei (1991) 17 Speiss (1990) 18 Hailwood and Clement (1991)

Basic information about the locations, water depths, age coverage and sedimentation rates is available in Table 1 and Fig. 4 and 5. All of the sites for this study were selected because they have been extensively studied and literature exists that documents subsidence histories, stable isotopic records and records of sedimentary parameters, such as clay mineralogy, biogenic carbonate and opal content and accumulation rates, carbonate preservation, and estimates of export production (see Tables 1 and 2 for information and relevant references).

11 Fig. 5 Sediment coverage and distribution of hiatuses for ODP sites 689, 690 and 699 corrected to the time scale by Cande and Kent (1995). Samples for this study will range from 46 to 28 Ma.

Water Masses and Nd

To reconstruct water circulation patterns in the Southern Ocean from Nd isotopic records we need the isotopic values for different potential end-member water masses and those values must be analytically distinct. Values for modern and paleo- water masses are listed in Table 3. There are only five published records of Nd isotopes from the Eocene/Oligocene, and these are low-resolution records (Fig. 6). In contrast, Scher and Martin (submitted) have compiled high-resolution records from fish teeth for two sites in the Southern Ocean: site 689 (Fig. 7) (Scher and Martin, submitted) and site 1090 in the Cape Basin (Martin and Scher, 2004). Based on these seven records we can make some estimates of the end-member isotopic composition of several water masses, but work from this proposal is required to refine these estimates. It is apparent from Table 3 that deep waters produced in the Mediterranean/Tethys region have been less radiogenic than

Southern Ocean waters by at least 0.5 Nd units today and in the past. Our external error on Nd analyses is +/-0.23; thus, we are able to analytically distinguish potential WSDW from SCW.

12 Table 3. Nd values for modern and Eocene water masses.

Modern Eocene (~40 Ma)

Water Mass Nd Water Mass Nd PDW -4 1 PDW -4.5 6 NADW -13.5 2 NCW -10.5 7,8 MOW -9.4 3 Tethys/WSDW -9.2 to -9.7 9 >-9.5 10 AABW -8 to -9 4,5 SCW -6 to -9 10,11 AAIW -7 to -9 4,5 CPW -6 to -9 5 Modern Values 1 Pacific Deep Water, Piepgras and Jacobsen, 1988 2 North Atlantic Deep Water, Piepgras and Wasserburg, 1987 3 Mediterranean Outflow Water, Spivack and Wasserburg, 1988 4 Antarctic Bottom Water, Jeandel, 1993; Albarede et al., 1997 5 Antarctic Intermediate Water, Jeandel, 1993; Albarede et al., 1997 Eocene Values (~40 Ma) 6 Pacific Deep Water, Ling et al., 1997 7 Northern Component Water, Burton et al., 1997 8 Northern Component Water, Burton et al., 1999 9 Tethys Water, Stille and Fisher, 1990 10 Warm Saline Deep Water, Southern Component Water, Scher and Martin, submitted 11 Southern Component Water, Martin and Scher, 2004

The Tethyan Nd values reported in Stille and Fischer (1990) (Table 3) come from authigenic glauconites in the Helvetic belt of the Alps, which are believed to have been deposited on the northern continental shelf of the extinct Tethys Ocean. Nd isotopes through time are generally stratified with depth, with the most radiogenic values near the surface (O’Nions et al., 1997; Frank, 2002). Thus, deep water in the Tethys during the Eocene should have been less radiogenic than –9.2 to –9.7 (Fischer and Stille, 1990), and, Fig. 6 therefore, analytically distinct. PublishedNd(T) data from Fe-Mn oxide crusts and coatings. The shaded rectangle highlights the interval of interest for this 357 study.Multi-proxy The five Approach records with coverage Theduring quasi-conservative this interval are fromnature Ling of Nd et alisotopes implies that they contain a signature of both (1998) for the Pacific, Palmer and Elderfieldlarge-scale (1986) circulation for DSDP and more site 357local in weathering. the Isolating these two effects is critical South Atlantic, and Burton et al (1997 and 1999) for the North Atlantic. Figure modified from Frank (2002)

13 689 eNd(T)

-7 Fig. 7 Nd isotopic data vs. -7.5 age based on fossil fish teeth from site -8 689. This relatively ) T high resolution record ( d -8.5 will be part of the N e data set used for this study. Modified from -9 Scher and Martin (submitted). -9.5

-10 15 20 25 30 35 40 45 50 Ag e (Ma) for the application of Nd isotopes as water mass tracers. We are proposing a multi-proxy approach combining our Nd records with Pb isotopic records with pre-existing datasets of stable isotopes and sediment properties. None of these proxies stands alone. 18O, 13C, carbonate and opal preservation, and estimates of export production contain records of

14 the chemical and physical properties of the water mass, while clay mineralogy and Pb isotopes provide information about the style and sources of continental weathering. This combination of proxies can help us deconvolve the water mass and weathering signals. Scher and Martin (submitted) applied a similar approach at site 689 to argue that most of the Nd signal reflected water mass mixing. This conclusion is supported by a pilot study at site 689 (Blair, unpublished data) that documented variations in Nd isotopes unaccompanied by variations in Pb isotopes.

Sampling Strategy Most of the isotopic records will be produced from leachates of Fe-Mn oxide coatings from the >63m fraction of the sediment with a resolution of one sample every 200 kyr from 44 to 28 Ma. The coatings are a relatively new archive for Nd isotopes on Eocene/Oligocene time scales, but they are readily available, require minimal preparation time, and incorporate high concentrations of Pb as well. As a continued test of the integrity of the oxide coatings we will also analyze fossil fish teeth every 2 myr. If we encounter problems with the Fe-Mn coatings we can always resort to the more labor- intensive fossil fish teeth for Nd isotopes.

Disregarding hiatuses, this sampling strategy translates to ~160 Nd isotopic analyses of coatings, ~18 Nd analyses of fish teeth, and ~240 Pb isotopic analyses. Although there are hiatuses, we will need to run replicates and the fish teeth samples, therefore these numbers represent a minimum estimate; actual analyses are estimated at 200 Nd and 275 Pb samples.

Analytical Methods Fossil fish teeth are hand picked from the >125 m fraction of dried, disaggregrated and sieved sediment. The teeth are cleaned using the oxidative/reductive cleaning technique from Boyle (1981), Boyle and Keigwin (1985) and Boyle (pers. comm., 1993) to chemically remove Fe-Mn oxide coatings, thereby yielding isotopic ratios derived purely from the teeth. Nd concentrations are ~200 ppm. Therefore, we need ~40 g of cleaned teeth (~1-2 teeth).

15 The Fe-Mn oxide coatings are leached from the >63m fraction of ODP sediment (Blair et al., 2004) using a procedure modified from Chester and Hughes (1967), Rutberg et al. (2000) and Bayon et al. (2002). Carbonate is removed by repeated dissolution in buffered acetic acid. These coatings are reduced using 0.02M hydroxylamine hydrochloride in 25% glacial acetic acid. The sample is placed on a wrist action shaker for 1 hour, then centrifuged and the supernate is decanted and split into two fractions for Nd and Pb isotopic analyses, which are dried down for column chemistry.

Nd is separated from both types of samples using two sequential cation exchange columns. The first column separates the bulk rare earth elements (REE) from other cations using Mitsubishi resin and HCl as an eluent. The REE cut is dried down and loaded onto a second Mitsubishi resin column and Nd is isolated using methylactic acid. The total procedural blank is 10 pg Nd.

The smaller Nd samples for the teeth are analyzed in dynamic mode on a Micromass Sector 54 thermal ionization mass spectrometer (TIMS) at the UF at a recharge rate of $35/sample. These small samples are analyzed as NdO, which significantly increases the efficiency. The samples are loaded on zone-refined Re filaments with silica gel. All ratios are normalized to 146Nd16O/144Nd/16O = 0.722254. Using 142Nd/16O as a monitor peak, beams of 0.5V are measured for 200 ratios. The 143Nd/144Nd value for repeat analyses of the international Nd standard JNdi-1 is 0.512102 (+/-0.000012, 2 external reproducibility, n=65). This uncertainty translates to 0.24 Nd units.

The larger oxide coating samples are analyzed on a Nu Plasma MC-ICP-MS at UF. Sample and standard solutions are aspirated into the plasma source via a Micromist desolvating nebulizer with a GE spray chamber (wet plasma). Preamplified gains are run before each analytical session. All ratios are normalized to 146Nd/144Nd = .7129 to correct for instrumental mass bias. Baselines are measured by ESA (electrostatic analyzer) deflection of the beam. Typical beam sizes for leachate runs are 5-10 V of total Nd. Our

16 143Nd/144Nd value for repeat analyses of the JNdi-1 standard is 0.512110 +/- 0.000014 (2).

Pb is separated from the Fe-Mn oxides using Teflon microcolumns and HBr as an eluent

(modified from Manhes,1978). The Pb cut is dried, diluted with 2% HNO3 and introduced into the Nu as for Nd. The isotope ratios are collected in static mode and normalized using 205Tl/203Tl = 2.38750 (Belshaw, 1998). The SRM 981 standard is run between every other sample. Values vary slightly with the tuning of the instrument, but 42 analyses in April-June, 2003 yielded 206Pb/204Pb = 16.9369 (+0.0039, 2), 207Pb/204Pb = 15.4904 (+0.0034, 2),208Pb/204Pb = 36.6949 (+0.0087, 2). We can run ~3 unknowns/hour on the Nu at a recharge rate of $50/hour.

Summary The goal of this proposal is to generate high resolution Nd and Pb isotope records for the middle Eocene through early Oligocene at three sites in the Atlantic sector of the Southern Ocean and compare these data to existing data including stable isotopes and sediment composition in order to determine:

 Whether there was a water mass with distinct Nd isotopes on Maud Rise during times of purported WDSW.

 The Nd value of WSDW, if it exists, compared to SCW.  The changes in weathering associated with dramatic changes in climate at the Eocene/Oligocene boundary.  The vertical extent of WSDW. In particular, whether it extends into the deep ocean at site 699 or is composed of a tongue of intermediate water that is only observed at site 690 and possibly 689.

Broader questions to be addressed include:  The nature of the connection between circulation and climate. Do changes in ocean circulation drive changes in climate or do changes in climate drive changes in ocean circulation?

17  The evolution of the Antarctic Circumpolar Current (ACC). Data from site 689 suggest the introduction of water into the South Atlantic with a Pacific Nd isotopic signature at least as early as the earliest estimates for the opening of the Drake Passage Lawver and Gahagan, 2004). The convergence of Nd isotopic values from various depths might indicate the onset of the ACC circulation.

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