Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Geochemistry and isotopes at DSDP Site 68-503

Nodules occur in the siliceous calcareous ooze and siliceous marl at Site 503 in the eastern equatorial Pacific. They are present below a depth of about 11 meters throughout the green-colored reduced part of the section down to 228 meters, although they are most abundant between 30 and 85 meters. They are cylindrical or barrel-shaped, up to 70 mm long, and usually have an axial channel through them or are hollow. They appear to have formed around and/or within burrows. XRD studies and microprobe analyses show that they are homogeneous and consist of calcian rhododrosite and minor calcite; Mn is present to the extent of about 30%. Isotopic analyses of the carbonate give carbon values which range from -1.2 per mil to -3.8 per mil, and oxygen isotope compositions vary from +4.0 per mil to +6.0 per mil. These values are different from those for marine-derived carbonates as exemplified by the soft sediment filling of a burrow: d13C, -0.26 per mil; d18O, +1.05 per mil. The carbon isotope data indicate that carbonate derived (possibly indirectly) from seawater was mixed with some produced by organic diagenesis to form the nodules. The d18O values suggest that although they formed near the sediment surface, some modification or the introduction of additional diagenetic carbonate occurred during burial.

Dissolved inorganic carbon isotopes in pore waters of ODP Leg 204 sediments

Isotopic characterization of carbon in the dissolved inorganic carbon (DIC) pool is fundamental for a wide array of scientific studies directly related to gas hydrate research. In order to generate integrated and internally consistent data of d13C of DIC in pore waters from Hydrate Ridge, we used the modern continuous flow technology of a GasBench II automated sampler interfaced to a gas source stable isotope mass spectrometer for the rapid determination (~80 samples/day) of d13C DIC in small-volume water samples. The overall precision of this technique is conservatively estimated to be better than ±0.15 per mil (1 sigma), which is similar to the precision of methods in current use. Here we present the data generated from Ocean Drilling Program Leg 204 pore water samples.

Stable isotope record of the Okhotsk Sea

Stable isotope data on benthic foraminifera from more than 30 cores on the northern Emperor Seamounts and in the Okhotsk Sea are synthesized in paleohydrographic profiles spanning the depth range 1000-4000 m. Holocene (core-top) benthic foraminiferal d18O and d13C data are calibrated to modern hydrographic properties through measurements of d13C of SumCO2 and d18O of seawater. Cibicidoides stable isotope ratios are close to the d13C and equilibrium d18O of seawater, whereas Uvigerina d18O and d13C are variably offset from Cibicidoides. Glacial maximum d13C of Cibicidoides displays a different vertical profile than that of the Holocene. When results are adjusted by +0.32 per mil to account for the secular change in d13C during the last glacial maximum, the data coincide with the modern seawater and foraminiferal curves deeper than ~2 km. However, at shallower depths d13C gradually increases by as much as 1 per mil above the modern value. Furthermore, above 2 km the benthic d18O decreases by ~0.5 per mil. These results are consistent with a benthic front at ~2 km in the North Pacific (see Herguera et al., 1992), but they differ from interpretations based on trace metal data which indicate a source of nutrient-depleted deep water during glaciation. The isotopic data suggest that during glaciation there was a better ventilated watermass at intermediate depths in the far northwestern Pacific, it was relatively fresher than deep waters there, and deep waters were as nutrient-rich as today.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

Stable carbon and oxygen isotope ratios for different test sizes of live benthic foraminifera from the Arabian Sea

We determined the stable oxygen and carbon isotopic composition of live (Rose Bengal stained) tests belonging to different size classes of two benthic foraminiferal species from the Pakistan continental margin. Samples were taken at 2 sites, with water depth of about 135 and 275 m, corresponding to the upper boundary and upper part of the core region of the oxygen minimum zone (OMZ). For Uvigerina ex gr. U. semiornata and Bolivina aff. B. dilatata, delta13C and delta18O values increased significantly with increasing test size. In the case of U. ex gr. U. semiornata, delta13C increased linearly by about 0.105 per mil for each 100-µm increment in test size, whereas delta18O increased by 0.02 to 0.06 per mil per 100 µm increment. For B. aff. B. dilatata the relationship between test size and stable isotopic composition is better described by logarithmic equations. A strong positive linear correlation is observed between delta18O and delta13C values of both taxa, with a constant ratio of delta18O and delta13C values close to 2:1. This suggests that the strong ontogenetic effect is mainly caused by kinetic isotope fractionation during CO2 uptake. Our data underline the necessity to base longer delta18O and delta13C isotope records derived from benthic foraminifera on size windows of 100 µm or less. This is already common practice in down-core isotopic studies of planktonic foraminifera.

(Table S3) Benthic foraminiferal Mg/Ca, Li/Ca and stable isotope ratios of ODP Site 122-761

The sensitivities of benthic foraminiferal Mg/Ca and Li/Ca to bottom water temperature and carbonate saturation state have recently been assessed. Here we present a new approach that uses paired Mg/Ca and Li/Ca records to calculate simultaneous changes in temperature and saturation state. Using previously published records, we first use this approach to document a cooling of deep ocean waters associated with the establishment of the Antarctic ice sheet at the Eocene-Oligocene climate transition. We then apply this approach to new records of the Middle Miocene Climate Transition from ODP Site 761 to estimate variations in bottom water temperature and the oxygen isotopic composition of seawater. We estimate that the oxygen isotopic composition of seawater varied by ~1 per mil between the deglacial extreme of the Miocene Climatic Optimum and the glacial maximum following the Middle Miocene Climate Transition, indicating large amplitude variations in ice volume. However, the longer-term change between 15.3 and 12.5 Ma is marked by a ~1°C cooling of deep waters, and an increase in the oxygen isotopic composition of seawater of ~0.6 per mil. We find that bottom water saturation state increased in the lead up to the Middle Miocene Climate Transition and decreased shortly after. This supports decreasing pCO2 as a driver for global cooling and ice sheet expansion, in agreement with existing boron isotope and leaf stomatal index CO2 records but in contrast to the published alkenone CO2 records.

Stable oxygen isotope ratios in zircons from oceanic crust

Lower ocean crust is primarily gabbroic, although 1-2% felsic igneous rocks that are referred to collectively as plagiogranites occur locally. Recent experimental evidence suggests that plagiogranite magmas can form by hydrous partial melting of gabbro triggered by seawater-derived fluids, and thus they may indicate early, high-temperature hydrothermal fluid circulation. To explore seawater-rock interaction prior to and during the genesis of plagiogranite and other late-stage magmas, oxygen-isotope ratios preserved in igneous zircon have been measured by ion microprobe. A total of 197 zircons from 43 plagiogranite, evolved gabbro, and hydrothermally altered fault rock samples have been analyzed. Samples originate primarily from drill core acquired during Ocean Drilling Program and Integrated Ocean Drilling Program operations near the Mid-Atlantic and Southwest Indian Ridges. With the exception of rare, distinctively luminescent rims, all zircons from ocean crust record remarkably uniform d18O with an average value of 5.2 ± 0.5 per mil (2SD). The average d18O(Zrc) would be in magmatic equilibrium with unaltered MORB [d18O(WR) ~5.6-5.7 per mil], and is consistent with the previously determined value for equilibrium with the mantle. The narrow range of measured d18O values is predicted for zircon crystallization from variable parent melt compositions and temperatures in a closed system, and provides no indication of any interactions between altered rocks or seawater and the evolved parent melts. If plagiogranite forms by hydrous partial melting, the uniform mantle-like d18O(Zrc) requires melting and zircon crystallization prior to significant amounts of water-rock interactions that alter the protolith d18O. Zircons from ocean crust have been proposed as a tectonic analog for >3.9 Ga detrital zircons from the earliest (Hadean) Earth by multiple workers. However, zircons from ocean crust are readily distinguished geochemically from zircons formed in continental crustal environments. Many of the >3.9 Ga zircons have mildly elevated d18O (6.0-7.5 per mil), but such values have not been identified in any zircons from the large sample suite examined here. The difference in d18O, in combination with newly acquired lithium concentrations and published trace element data, clearly shows that the >3.9 Ga detrital zircons did not originate by processes analogous to those in modern mid-ocean ridge settings.

Stable isotope record of Cibicidoides spp. from Late Miocene sediments of the Southern Ocean

Deepwater circulation plays an important role in climate modulation through its redistribution of heat and salt and its control of atmospheric CO2. Oppo and Fairbanks (1987, doi:10.1016/0012-821X(87)90183-X) showed that the Southern Ocean is an excellent monitor of deepwater circulation changes for two reasons: (1) the Southern Ocean is a mixing reservoir for incoming North Atlantic Deep Water and recirculated water from the Pacific and Indian oceans; and (2) the nutrient/delta13C tracers of deepwater are not significantly changed by surficial processes within the Southern Ocean. We can extend these principles to the late Miocene because tectonic changes in the Oligocene and early and middle Miocene developed near-modern basinal configurations. However, on these time scales, changes in the oceanic carbon reservoir and mean ocean nutrient levels also affect the delta13C differences between ocean basins. From 9.8 to 9.3 Ma, Southern Ocean delta13C values oscillated between high North Atlantic values and low Pacific values. The Southern Ocean recorded delta13C values similar to Pacific values from 9.2 to 8.9 Ma, reflecting a low contribution of Northern Component Water (NCW). The delta13C differences between the NCW and Pacific Outflow Water (POW) end-members were low from 8.9 to 8.0 Ma, making it difficult to discern circulation patterns. NCW production may have completely shutdown at 8.6 Ma, allowing Southern Component Water (SCW) to fill the North Atlantic and causing the delta13C values in the North Atlantic, Pacific, and Southern oceans to converge. Deepwater delta13C patterns resembling the modern distributions evolved by 7.0 Ma: delta13C values were near 1.0 per mil in the North Atlantic; 0.0 per mil in the Pacific; and 0.5 per mil in the Southern Ocean. Development of near-modern delta13C distributions by 7.0 Ma resulted not only from an increase in NCW flux but also from an increase in deepwater nutrient levels. Both of these processes increased the delta13C difference between the North Atlantic and Pacific oceans. Deepwater circulation patterns similar to today's operated as early as 9.8 Ma, but were masked by the lower nutrient/delta13C differences. During the late Miocene, 'interglacial' intervals prevailed during intervals of NCW production, while 'glacial' intervals occurred during low NCW production.

Stable isotopes and ages from sediment core FR01/97-12, Tasman Sea

Deep-sea sediment core FR1/97 GC-12 is located 990 mbsl in the northern Tasman Sea, southwest Pacific, where Antarctic Intermediate Water (AAIW) presently impinges the continental slope of the southern Great Barrier Reef. Analysis of carbon (d13C) and oxygen (d18O) isotope ratios on a suite of planktonic and benthic foraminifera reveals rapid changes in surface and intermediate water circulation over the last 30 kyr. During the Last Glacial Maximum, there was a large d13C offset (1.1 per mil) between the surface-dwelling planktonic foraminifera and benthic species living within the AAIW. In contrast, during the last deglaciation (Termination 1), the d13C(planktonic-benthic) offset reduced to 0.4 per mil prior to an intermediate offset (0.7 per mil) during the Holocene. We suggest that variations in the dominance and direction of AAIW circulation in the Tasman Sea, and increased oceanic ventilation, can account for the rapid change in the water column d13C(planktonic-benthic) offset during the glacial-interglacial transition. Our results support the hypothesis that intermediate water plays an important role in propagating climatic changes from the polar regions to the tropics. In this case, climatic variations in the Southern Hemisphere may have led to the rapid ventilation of deep water and AAIW during Termination 1, which contributed to the postglacial rise in atmospheric CO2.

Geochemistry of carbonate cements of ODP Leg 112 samples

The evolution of pore fluids migrating through the forearc basins, continental massif, and accretionary prism of the Peru margin is recorded in the sequence of carbonate cements filling intergranular and fracture porosities. Petrographic, mineralogic, and isotopic analyses were obtained from cemented clastic sediments and tectonic breccias recovered during Leg 112 drilling. Microbial decomposition of the organic-rich upwelling facies occurs during early marine diagenesis, initially by sulfate-reduction mechanisms in the shallow subsurface, succeeded by carbonate reduction at depth. Microcrystalline, authigenic cements formed in the sulfate-reduction zone are 13C-depleted (to -20.1 per mil PDB), and those formed in the carbonate-reduction zone are 13C-enriched (to +19.0 per mil PDB). Calcium-rich dolomites and near-stoichiometric dolomites having uniformly heavy d18O values (+2.7 to +6.6 per mil PDB) are typical organic decomposition products. Quaternary marine dolomites from continental-shelf environments exhibit the strongest sulfate-reduction signatures, suggesting that Pleistocene sea-level fluctuations created a more oxygenated water column, caused periodic winnowing of the sediment floor, and expanded the subsurface penetration of marine sulfate. We have tentatively identified four exotic cement types precipitated from advected fluids and derived from the following diagenetic environments: (1) meteoric recharge, (2) basalt alteration, (3) seafloor venting and (4) hypersaline concentration. Coarsely crystalline, low-magnesium (Lo-Mg) calcite cements having pendant and blocky-spar morphologies, extremely negative d18O values (to -7.5 per mil PDB), and intermediate d13C values (-0.4 per mil to +4.6 per mil PDB) are found in shallow-marine Eocene strata. These cements are evidently products of meteoric diagenesis following subaerial emergence during late Eocene orogenic movements, although the strata have since subsided to greater than 4,000 m below sea level. Lo-Mg calcite cements filling scaly fabrics in the late Miocene accretionary prism sediments are apparently derived from fluids having lowered magnesium/calcium (Mg/Ca) and 18O/16O ratios; such fluids may have reacted with the subducting oceanic crust and ascended through the forearc along shallow-dipping thrust faults. Micritic, high-magnesium (Hi-Mg) calcite cements having extremely depleted d13C values (to -37.3%c PDB), and a benthic fauna of giant clams (Calyptogena sp.) supported by a symbiotic, chemoautotrophic metabolism, provide evidence for venting of methane-charged waters at the seafloor. Enriched d18O values (to +6.6%c PDB) in micritic dolomites from the continental shelf may be derived from hypersaline fluids that were concentrated in restricted lagoons behind an outer-shelf basement ridge, reactivated during late Miocene orogenesis.

Stable isotope record of Cibicidoides spp. from early and middle Miocene sediments

The middle Miocene delta18O increase represents a fundamental change in the ocean-atmosphere system which, like late Pleistocene climates, may be related to deepwater circulation patterns. There has been some debate concerning the early to early middle Miocene deepwater circulation patterns. Specifically, recent discussions have focused on the relative roles of Northern Component Water (NCW) production and warm, saline deep water originating in the eastern Tethys. Our time series and time slice reconstructions indicate that NCW and Tethyan outflow water, two relatively warm deepwater masses, were produced from ~20 to 16 Ma. NCW was produced again from 12.5 to 10.5 Ma. Another feature of the early and middle Miocene oceans was the presence of a high delta13C intermediate water mass in the southern hemisphere, which apparently originated in the Southern Ocean. Miocene climates appear to be related directly to deepwater circulation changes. Deep-waters warmed in the early Miocene by ~3°C (?20 to 16 Ma) and cooled by a similar amount during the middle Miocene delta18O increase (14.8 to 12.6 Ma), corresponding to the increase (?20 Ma) and subsequent decrease (~16 Ma) in the production of NCW and Tethyan outflow water. Large (>0.6 per mil), relatively rapid (~0.5 m.y.) delta18O increases in both benthic and planktonic foraminifera (i.e., the Mi zones of Miller et al. (1991a) and Wright and Miller (1992a)) were superimposed in the long-term deepwater temperature changes; they are interpreted as reflecting continental ice growth events. Seven of these m.y. glacial/interglacial cycles have been recognized in the early to middle Miocene. Two of these glacial/interglacial cycles (Mi3 and Mi4) combined with a 2° to 3°C decrease in deepwater temperatures to produce the middle Miocene delta18O shift.

Sea surface temperature reconstruction for sediment core KNO5103-0029GGC

We present a 15 kyr sea surface temperature (SST) record for a high sedimentation rate core (KNR51-29GGC) from the Feni Drift off of Ireland, based on an organic geochemical technique for paleotemperature estimation, U37 K'. We compare the U37 K' temperature record to planktonic foraminiferal delta18O and foraminiferal assemblage SST estimates from the same sample horizons. U37 K' gives SST estimates of 13°C for the early deglacial and 18°C for the Holocene and Recent, whereas assemblages give estimates of 9°C and 13°C, respectively. As in nearby core V23-81, we find Ash Zone 1, the Younger Dryas increase in Neogloboquadrina pachyderma sinistral abundance, and maximum abundance of this species during glaciation. N. pachyderma dextral oxygen isotopic analyses have a late glacial to interglacial range of 1.5 per mil. A reduction of about 1 per mil in delta18O occurred at about 12 ka, whereas U37 K' and the foraminiferal fauna indicate a 2°C warming. This implies a 0.9 per mil salinity effect on delta18O which we attribute to meltwater freshening. All three parameters indicate cooling during the Younger Dryas. U37 K' SST estimates show that the major shift from deglacial to interglacial temperatures occurred after the Younger Dryas in termination 1b, in contrast to the assemblage data, which show this jump in SST at the end of the glaciation during termination Ia. Differences between the two SST estimators, which may result from their different (floral versus faunal) sources, are more pronounced between transitions Ia and Ib. This may reflect different habitats under the unusual sea surface conditions of the deglaciation.

Middle Miocene stable carbon and oxygen isotope record of foraminifera of ODP Hole 120-747A

Paleoceanographic variability at southern high latitude Ocean Drilling Program (ODP) Site 747 was investigated in this study through the interval which spans the Middle Miocene Climate Transition (MMCT). Between 15.0 and 12.2 million years ago (Ma), foraminiferal d18O records derived from both benthic (Cibicidoides spp.) and planktonic taxa (Globorotalia praescitula and Globigerina bulloides) reveal a history of changes in water column thermal and salinity structure and a strong imprint of seasonality. Prior to the MMCT, in the interval between 14.35 and 13.9 Ma, G. bulloides displays relatively high d18O values similar to those of G. praescitula, interpreted to indicate weakening of the thermocline and/or increased seasonality with cooler early-spring and/or late-fall temperatures. Following this interval, G. bulloidesd18O values diverge significantly from benthic and G. praescitula values, with G. bulloides values remaining relatively low for at least 600 kyr following the benthic foraminiferal d18O shift during the MMCT at ~13.9 Ma. This divergence in d18O records occurs in direct association with the Mi3 cooling and glaciation event and may suggest: (1) a strengthening of the vertical temperature gradient, with greater cooling of deep waters than surface waters, (2) changes in the depth habitat of G. bulloides, (3) changes in the dominant season of G. bulloides calcification, (4) modification of surface-water d18O values in association with enhanced sea-ice formation, (5) increased surface-water carbonate ion concentration, and/or (6) a significant decrease in surface-water salinity across the MMCT. The first of these possible scenarios is not likely, particularly in light of recent Mg/Ca evidence for significant surface-water cooling in the Southern Ocean associated with the MMCT. Of the remaining possibilities, we favor a change in surface salinity to explain the observed trends in d18O values and hypothesize that surface salinity may have decreased by up to 2 salinity units at ~13.9 Ma. In this scenario, the development of a lower-salinity Antarctic surface layer coincided with regional cooling of both surface and deep waters of the Southern Ocean during the Mi3 glaciation of East Antarctica, and contributed into the dominance of Neogloboquadrina spp. between 13.8 and 13.2 Ma. Additionally, the distinct patterns observed in planktonic foraminiferal d18O records spanning the MMCT correspond with changes in the vertical d13C gradient between planktonic and benthic foraminiferal records and major changes in planktonic foraminiferal assemblages at Site 747, providing further evidence of the environmental significance of this climatic transition.

Benthic foraminiferal biofacies and stable isotopic record of St. Stephens Quarry, Alabama

We integrate upper Eocene-lower Oligocene lithostratigraphic, magnetostratigraphic, biostratigraphic, stable isotopic, benthic foraminiferal faunal, downhole log, and sequence stratigraphic studies from the Alabama St. Stephens Quarry (SSQ) core hole, linking global ice volume, sea level, and temperature changes through the greenhouse to icehouse transition of the Cenozoic. We show that the SSQ succession is dissected by hiatuses associated with sequence boundaries. Three previously reported sequence boundaries are well dated here: North Twistwood Creek-Cocoa (35.4-35.9 Ma), Mint Spring-Red Bluff (33.0 Ma), and Bucatunna-Chickasawhay (the mid-Oligocene fall, ca. 30.2 Ma). In addition, we document three previously undetected or controversial sequences: mid-Pachuta (33.9-35.0 Ma), Shubuta-Bumpnose (lowermost Oligocene, ca. 33.6 Ma), and Byram-Glendon (30.5-31.7 Ma). An ~0.9 per mil d18O increase in the SSQ core hole is correlated to the global earliest Oligocene (Oi1) event using magnetobiostratigraphy; this increase is associated with the Shubuta-Bumpnose contact, an erosional surface, and a biofacies shift in the core hole, providing a first-order correlation between ice growth and a sequence boundary that indicates a sea-level fall. The d18O increase is associated with a eustatic fall of ~55 m, indicating that ~0.4 per mil of the increase at Oi1 time was due to temperature. Maximum d18O values of Oi1 occur above the sequence boundary, requiring that deposition resumed during the lowest eustatic lowstand. A precursor d18O increase of 0.5 per mil (33.8 Ma, midchron C13r) at SSQ correlates with a 0.5 per mil increase in the deep Pacific Ocean; the lack of evidence for a sea-level change with the precursor suggests that this was primarily a cooling event, not an ice-volume event. Eocene-Oligocene shelf water temperatures of ~17-19 °C at SSQ are similar to modern values for 100 m water depth in this region. Our study establishes the relationships among ice volume, d18O, and sequences: a latest Eocene cooling event was followed by an earliest Oligocene ice volume and cooling event that lowered sea level and formed a sequence boundary during the early stages of eustatic fall.