Stable isotope and Magnesium/Calcium ratios of 4 profiles from the equatorial Pacific/Caribbean

This thesis examines the closure history of the Central American Seaway (CAS) and its effect on changes in ocean circulation and climate during the time interval from ~6 - 2.5 Ma. It was accomplished within the DFG Research Unit "Impact of Gateways on Ocean Circulation, Climate and Evolution" at the University of Kiel. Proxy records from Ocean Drilling Program (ODP) Sites 999 and 1000 (Caribbean), and from ODP Sites 1237, 1239 and 1241 (low-latitude east Pacific) are developed and examined. In addition, previously established proxy data from Atlantic Sites 925/926 (Ceara Rise) and 1006 (western Great Bahama Bank) and from two east Pacific sites (851, 1236) are included for interpretations. The main objectives of this study are (1) to acquire a consistent stratigraphic framework for all sites, (2) to reconstruct Pliocene changes in Caribbean and tropical east Pacific upper ocean water masses (i.e. temperature, salinity, thermocline depth), and (3) to identify potential underlying forcing mechanisms.

Age model and stable isotope record of eastern equatorial Pacific sediment cores

Six deep sea cores from the eastern equatorial Pacific (EEP) were analyzed for planktonic foraminifera and stable isotopes in order to reconstruct sea surface temperatures (SST) for the last 40 ka. South of the Equatorial Front the abundance of Globorotalia inflata increased, and SST decreased by >5°C (core ODP846B), creating a stronger SST meridional gradient and advection of the Peru Current than present for the ~16-35 ka interval. A sharper SST meridional gradient forced stronger Choco jet events and a moisture increase in western Colombia, which supplied, through the San Juan River and the south-flowing equatorial and the Peru-Chile countercurrents, abundant hemipelagic quartz over the northern Peru basin (core TR163-31B). The Choco jet, and its associated mesoscale convective cells, provoked an increase in snow precipitation over the Central Cordillera of Colombia and the advance of the Murillo glacier. In synchrony with the intensified Choco jet events, the "dry island" effect over the Eastern Cordillera of Colombia intensified, and the level of Fuquene Lake dropped.

Planktonic foraminifera in the trans-tropical Pacific Ocean

Cores from four Ocean Drilling Program (ODP) sites were examined for planktonic foraminifers. One sample per core (from core-catchers in Holes 806B and 807B and from Section 4 in Holes 847B and 852B) was examined through the interval representing the last 5.8 m.y. Sites 806 (0°19.1'N; 159°21.7'E) and 847 (0o12.1'N; 95°19.2'W) are beneath the equatorial divergence zone. Sites 807 (3°36.4'N; 156°37.5'E) and 852 (5°19.6'N; 110°4.6'W) are located north of the equator in the convergence zone created by the interaction of the westward-flowing South Equatorial Current (SEC) and the eastward-flowing North Equatorial Countercurrent (NECC). Specimens were identified to species and then grouped according to depth habitat and trophic level. Species richness and diversity were also calculated. Tropical neogloboquadrinids have been more abundant in the eastern than in the western equatorial Pacific Ocean throughout the last 5.8 m.y. During the mid-Pliocene (3.8-3.2 Ma), their abundance increased at all sites, while during the Pleistocene (after ~ 1.6 Ma), they expanded in the east and declined in the west. This suggests an increase in surface-water productivity across the Pacific Ocean during the closing of the Central American seaway and an exacerbation of the productivity asymmetry between the eastern and western equatorial regions during the Pleistocene. This faunal evidence agrees with eolian grain-size data (Hovan, 1995) and diatom flux data (Iwai, this volume), which suggest increases in tradewind strength in the eastern equatorial Pacific that centered around 3.5 and 0.5 Ma. The present longitudinal zonation of thermocline dwelling species, a response to the piling of warm surface water in the western equatorial region of the Pacific, seems to have developed after 2.4 Ma, not directly after the closing of the Panama seaway (3.2 Ma). Apparently, after 2.4 Ma, the piling warm water in the west overwhelmed the upwelling of nutrients into the photic zone in that region, creating the Oceanographic asymmetry that exists in the modern tropical Pacific and is reflected in the microfossil record. In the upper Miocene and lower Pliocene sediments, the ratio of thermocline-dwelling species to mixed-layer dwellers is 60%:40%. During the mid-Pliocene, the western sites became 40% thermocline and 60% mixed-layer dwellers. Subsequent to -2.4 Ma, the asymmetry increased to 20%: 80% in the west and the reverse in the east. This documents the gradual thickening of the warm-water layer piled up in the western tropical Pacific over the last 5.8 m.y. and reveals two "steps" in the biotic trend that can be associated with specific events in the physical environment.

Sea surface fugacity of carbon dioxide measurements in the Pacific ocean

As part of the JGOFS field program, extensive CO2 partial-pressure measurements were made in the atmosphere and in the surface waters of the equatorial Pacific from 1992 to 1999. For the first time, we are able to determine how processes occurring in the western portion of the equatorial Pacific impact the sea-air fluxes of CO2 in the central and eastern regions. These 8 years of data are compared with the decade of the 1980s. Over this period, surface-water pCO2 data indicate significant seasonal and interannual variations. The largest decreases in fluxes were associated with the 1991-94 and 1997-98 El Niño events. The lower sea-air CO2 fluxes during these two El Niño periods were the result of the combined effects of interconnected large-scale and locally forced physical processes: (1) development of a low-salinity surface cap as part of the formation of the warm pool in the western and central equatorial Pacific, (2) deepening of the thermocline by propagating Kelvin waves in the eastern Pacific, and (3) the weakening of the winds in the eastern half of the basin. These processes serve to reduce pCO2 values in the central and eastern equatorial Pacific towards near-equilibrium values at the height of the warm phase of ENSO. In the western equatorial Pacific there is a small but significant increase in seawater pCO2 during strong El Niño events (i.e., 1982-83 and 1997-98) and little or no change during weak El Niño events (1991-94). The net effect of these interannual variations is a lower-than-normal CO2 flux to the atmosphere from the equatorial Pacific during El Niño. The annual average fluxes indicate that during strong El Niños the release to the atmosphere is 0.2-0.4 Pg C/yr compared to 0.8-1.0 Pg C/yr during non-El Niño years.

Distribution of diatoms in Oligocene to Pleistocene sediments of the tropical Pacific

According to the drilling probes of the Deep Waier Drilling Project, Neogene sediments in a tropical area of the Pacific Ocean are divided into 15 zones based on diatoms. The author shows that a unique zonation may be applied for the entire region. Identification of diatoms zones boundaries was conducted through their direct correlation with nannoplancton, radiolarian and foraminiferal zonal sceals. Their ultra-structure and morphological relationship are being analysed. The mode of siliceous accumulation within the equatorial belt differed through the western central and eastern region since the early Miocene and the difference become more evident from the end of Middle Miocene. The distribution of Neogene diatomaceous silt in the tropical area is controlled by the character of gyre-water circulation and agrees with the modern geographical zonation.

Composition of Fe-Mn minerals from island arcs of the West Pacific

This paper presents materials on the chemical and mineralogical composition of Fe-Mn mineralization in island arcs (Kuril, Nampo, Mariana, New Britain, New Hebrides, and Kermadec) in the western part of the Pacific Ocean. The mineralization was proved to be of hydrothermal and/or hydrogenic genesis. The former is produced by hydrothermal Fe and Mn oxi-hydroxides that cement volcanic-terrigenous material in sediments. Some Fe oxyhydroxides can be derived via the halmyrolysis of volcaniclastic material. Crusts of this stage are characterized by fairly low concentrations of trace and rare elements, and their REE composition is inherited from the volcanic-terrigenous material. The minerals of the Mn oxyhydroxides are todorokite and "Ca-birnessite". The Mn/Fe ratio increases away from the discharge sites of the hydrothermal solutions. The hydrogenic Fe-Mn crusts are characterized by high concentrations of trace and minor elements of both the Mn group (Co, Ni, Tl, and Mo) and the Fe group (REE, Y, and Th). The hydrogenic crusts consist of Fe-vernadite and Mn-feroxyhyte. Some of the hydrothermal crusts originally had a hydrothermal genesis. The first data were obtained on crust B30-72-10 from the Macauley Seamount in the Kermadec island arc, which contained anomalously high concentrations of Co (2587 ppm) and other Mn-related trace elements in the absence of hydrogeneous Fe oxyhydroxides.

Chemical composition of dredged rocks from the Hess Deep, Eastern Equatorial Pacific

A joint analysis of data on the anomalous magnetic field, seismicity, and structures of the Hess deep basalts have allowed to specify propagation of the spreading zone and to correct position of the neovolcanic zone. A precise petrogeochemical analysis of various types of basalts composing the uneven-aged oceanic crust of the basin showed that magmatics of the neovolcanic zone are related to the primitive type in contrast to rift boards of differential basalts. A model of the deep structure of the Galapagos rift in the area of the western Hess Deep has been suggested.

Palynology and dinoflagellate counts of surface sediments, and sea surface conditions, of sites in the North Pacific

Palynological analyses were performed on 53 surface sediment samples from the North Pacific Ocean, including the Bering and Okhotsk Seas (37-64°N, 144°E-148°W), in order to document the relationships between the dinocyst distribution and sea-surface conditions (temperatures, salinities, primary productivity and sea-ice cover). Samples are characterized by concentrations ranging from 18 to 143816 cysts/cm**3 and the occurrence of 32 species. A canonical correspondence analysis (CCA) was carried out to determine the relationship between environmental variables and the distribution of dinocyst taxa. The first and second axes represent, respectively, 47% and 17.8% of the canonical variance. Axis 1 is positively correlated with all parameters except to the sea-ice and primary productivity in August, which are on the negative side. Results indicate that the composition of dinocyst assemblages is mostly controlled by temperature and that all environmental variables are correlated together. The CCA distinguishes 3 groups of dinocysts: the heterotrophic taxa, the genera Impagidinium and Spiniferites as well as the cyst of Pentapharsodinium dalei and Operculodinium centrocarpum. Five assemblage zones can be distinguished: 1) the Okhotsk Sea zone, which is associated to temperate and eutrophic conditions, seasonal upwellings and Amur River discharges. It is characterized by the dominance of O. centrocarpum, Brigantedinium spp. and Islandinium minutum; 2) the Western Subarctic Gyre zone with subpolar and mesotrophic conditions due to the Kamchatka Current and Alaska Stream inflows. Assemblages are dominated by Nematosphaeropsis labyrinthus, Pyxidinopsis reticulata and Brigantedinium spp.; 3) the Bering Sea zone, depicting a subpolar environment, influenced by seasonal upwellings and inputs from the Anadyr and Yukon Rivers. It is characterized by the dominance of I. minutum and Brigantedinium spp.; 4) the Alaska Gyre zone with temperate conditions and nutrient-enriched surface waters, which is dominated by N. labyrinthus and Brigantedinium spp. and 5) the Kuroshio Extension-North Pacific-Subarctic Current zone characterized by a subtropical and oligotrophic environment, which is dominated by O. centrocarpum, N. labyrinthus and warm taxa of the genus Impagidinium. Transfer functions were tested using the modern analog technique (MAT) on the North Pacific Ocean (= 359 sites) and the entire Northern Hemisphere databases ( = 1419 sites). Results confirm that the updated Northern Hemisphere database is suitable for further paleoenvironmental reconstructions, and the best results are obtained for temperatures with an accuracy of +/-1.7 °C.

Chemical composition of volcanic glass of some tephra layers in Northeastern Pacific Ocean

Five widespread upper Cenozoic tephra layers that are found within continental sediments of the western United States have been correlated with tephra layers in marine sediments in the Humboldt and Ventura basins of coastal California by similarities in major-and trace-element abundances; four of these layers have also been identified in deep-ocean sediments at DSDP sites 34, 36, 173, and 470 in the northeastern Pacific Ocean. These layers, erupted from vents in the Yellowstone National Park area of Wyoming and Idaho (Y), the Cascade Range of the Pacific Northwest (C), and the Long Valley area, California (L), are the Huckleberry Ridge ash bed (2.0 Ma, Y), Rio Dell ash bed (ca. 1.5 Ma, C), Bishop ash bed (0.74 Ma, L), Lava Creek B ash bed (0.62 Ma, Y), and Loleta ash bed (ca. 0.4 Ma, C). The isochronous nature of these beds allows direct comparison of chronologic and climatic data in a variety of depositional environments. For example, the widespread Bishop ash bed is correlated from proximal localities near Bishop in east-central California, where it is interbedded with volcanic and glacial deposits, to lacustrine beds near Tecopa, southeastern California, to deformed on-shore marine strata near Ventura, southwestern California, to deep-ocean sediments at site 470 in the eastern Pacific Ocean west of northern Mexico. The correlations allow us to compare isotopic ages determined for the tephra layers with ages of continental and marine biostratigraphic zones determined by magnetostratigraphy and other numerical age control and also provide iterative checks for available age control. Relative age variations of as much as 0.5 m.y. exist between marine biostratigraphic datums [for example, highest occurrence level of Discoaster brouweri and Calcidiscus tropicus (= C. macintyrei)], as determined from sedimentation rate curves derived from other age control available at each of several sites. These discrepancies may be due to several factors, among which are (1) diachronism of the lowest and highest occurrence levels of marine faunal and floral species with latitude because of ecologic thresholds, (2) upward reworking of older forms in hemipelagic sections adjacent to the tectonically active coast of the western United States and other similar analytical problems in identification of biostratigraphic and magnetostratigraphic datums, (3) dissolution of microfossils or selective diagenesis of some taxa, (4) lack of precision in isotopic age calibration of these datums, (5) errors in isotopic ages of tephra beds, and (6) large variations in sedimentation rates or hiatuses in stratigraphic sections that result in age errors of interpolated datums. Correlation of tephra layers between on-land marine and deep-ocean deposits indicates that some biostratigraphic datums (diatom and calcareous nannofossil) may be truly time transgressive because at some sites, they are found above and, at other sites, below the same tephra layers.

Stable oxygen isotope. Mg/Ca and Temperature record of Caribbean and Pacific sediments

The final phase of the closure of the Panamanian Gateway and the intensification of Northern Hemisphere Glaciation (NHG) both occurred during the Late Pliocene. Glacial-interglacial (G-IG) variations in sea level might, therefore, have had a significant impact on the remaining connections between the East Pacific and the Caribbean. Here, we present combined foraminiferal Mg/Ca and d18O measurements from Ocean Drilling Program (ODP) Site 1241 from the East Pacific and ODP Site 999 from the Caribbean. The studied time interval covers the first three major G-IG Marine Isotope Stages (MIS 95-100, ~2.5 Ma) after the intensification of NHG. Analyses were performed on the planktonic foraminifera Neogloboquadrina dutertrei and Globigerinoides sacculifer, representing water mass properties in the thermocline and the mixed-layer, respectively. Changes in sea water temperature, relative salinity, and water column stratification strongly suggest that the Panamanian Gateway temporarily closed during glacial MIS 98 and 100, as a result of changes in ice volume equivalent to a drop in sea level of 60-90 m. Reconstructed sea surface temperatures (SST) from G. sacculifer show a glacial decrease of 2.5°C at Site 1241, but increases of up to 3°C at Site 999 during glacial MIS 98 and 100 suggesting that the Panamanian Gateway closed during these glacial periods. The Mg/Ca-temperatures of N. dutertrei remain relatively stable in the East Pacific, but do show a 3°C warming in the Caribbean at the onset of these glacial periods suggesting that the closing of the gateway also changed the water column stratification. We infer that the glacial closure of the gateway allowed the Western Atlantic Warm Pool to extend into the southern Caribbean, increasing SST (G. sacculifer) and deepening the thermocline (N. dutertrei). Additionally, ice volume appears to have become large enough during MIS 100 to survive the relatively short lasting interglacial MIS 99 so that the gateway remained closed. Towards the end of MIS 98, during MIS 97 and into MIS 96 temperatures on both sides are mostly similar suggesting water masses exchanged again. Additionally, Caribbean variations in SST and d18Owater follow a precession-like cyclicity rather than the obliquity-controlled variations characteristic of the East-Pacific and many other tropical areas, suggesting that regional atmospheric processes related to the trade winds and the Intertropical Convergence Zone (ITCZ) had a dominant impact in the Caribbean.

14C sedimentation rates and benthic mixing of equatorial Pacific sediments

Carbon-14 determinations on box cores of calcareous ooze from the western and eastern equatorial Pacific suggest that patterns of mixed-layer ages, sedimentation rates, and mixed-layer thicknesses are controlled by gradients of carbonate dissolution and fertility, and by small-scale redeposition processes. Mixed-layer ages range from 3000 to 7000 years, with a mode between 4000 and 5000 years. Sedimentation rates range from 0.8 to 2.4 cm/1000 years. Mixed-layer depths, calculated according to the box model of mixing, range from 7 cm to 16 cm. Observed thicknesses are about one-fourth smaller than calculated ones.

Chemical composition of rocks from the Kammu Seamount and from low atolls of the Western Indian Ocean

Devoted to studies of phosphatized rocks from the Kammu Seamount.

Nd and Sr isotope compositions, REE concentrations and Al/Ca ratios of different phases of surface sediments in the South Pacific

The radiogenic isotope composition of neodymium (Nd) and strontium (Sr) are useful tools to investigate present and past oceanic circulation or input of terrigenous material. We present Nd and Sr isotope compositions extracted from different sedimentary phases, including early diagenetic Fe-Mn coatings, "unclean" foraminiferal shells, fossil fish teeth, and detritus of marine surface sediments (core-tops) covering the entire midlatitude South Pacific. Comparison of detrital Nd isotope compositions to deep water values from the same locations suggests that "boundary exchange" has little influence on the Nd isotope composition of western South Pacific seawater. Concentrations of Rare Earth Elements (REE) and Al/Ca ratios of "unclean" planktonic foraminifera suggest that this phase is a reliable recorder of seawater Nd isotope composition. The signatures obtained from fish teeth and "nondecarbonated" leachates of bulk sediment Fe-Mn oxyhydroxide coatings also agree with "unclean" foraminifera. Direct comparison of Nd isotope compositions extracted using these methods with seawater Nd isotope compositions is complicated by the low accumulation rates yielding radiocarbon ages of up to 24 kyr, thus mixing the signal of different ocean circulation modes. This suggests that different past seawater Nd isotope compositions have been integrated in authigenic sediments from regions with low sedimentation rates. Combined detrital Nd and Sr isotope signatures indicate a dominant role of the Westerly winds transporting lithogenic material from South New Zealand and Southeastern Australia to the open South Pacific. The proportion of this material decreases toward the east, where supply from the Andes increases and contributions from Antarctica cannot be ruled out.

South Pacific dissolved Nd isotope compositions, rare earth element and nutrient concentrations from SONNE cruise SO213

Despite its enormous extent and importance for global climate, the South Pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography. Here we present the first detailed analysis of dissolved radiogenic Nd isotopes (epsilon-Nd) and rare earth elements (REEs) in intermediate and deep waters of the mid-latitude (~40°S) South Pacific along a meridional transect between South America and New Zealand. The goal of our study is to gain better insight into the distribution and mixing of water masses in the South Pacific and to evaluate the validity of Nd isotopes as a water mass tracer in this remote region of the ocean. The results demonstrate that biogeochemical cycling (scavenging processes in the Eastern Equatorial Pacific) and release of LREEs from the sediment clearly influence the distribution of the dissolved REE concentrations at certain locations. Nevertheless, the Nd isotope signatures clearly trace water masses including AAIW (Antarctic Intermediate Water) (average epsilon-Nd = -8.2 ± 0.3), LCDW (Lower Circumpolar Deep Water) (average epsilon-Nd = -8.3 ± 0.3), NPDW (North Pacific Deep Water) (average epsilon-Nd = -5.9 ± 0.3), and the remnants of NADW (North Atlantic Deep Water) (average epsilon-Nd = -9.7 ± 0.3). Filtered water samples taken from the sediment-water interface under the deep western boundary current off New Zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process. These data will serve as a basis for the paleoceanographic application of Nd isotopes in the South Pacific.

Chemical composition of East Pacific Rise basal sediments

Analyses by atomic absorption spectrophotometry and spark-source mass spectrography of 25 basal metalliferous sediment units from widely spaced locations on the western flank of the East Pacific Rise show that the deposits are enriched relative to normal pelagic sediment in Fe, Mn, Ni, Cu, Pb, Zn, and many trace elements. The elements are partitioned differently between the various mineralogic constituents of the sediment, with Fe and Mn largely in separate phases and many of the remaining elements primarily associated with reducible ferromanganese oxide minerals but also with iron minerals and other phases. Most of the iron in the deposits is probably of volcanic origin, and much of the manganese and minor elements is derived from sea water. The bulk composition of the deposits varies with age; this is thought to be due to variations in the incidence of volcanic activity at the East Pacific Rise crest where the deposits were formed.