Low-temperature magnetic remanence and hysteresis measurements on sediment core GeoB4901-8 from the Niger deep-sea fan

Low-temperature (LT) magnetic remanence and hysteresis measurements, in the range 300-5 K, were combined with energy dispersive spectroscopy (EDS) in order to characterize the magnetic inventory of strongly diagenetically altered sediments originating from the Niger deep-sea fan. We demonstrate the possibility of distinguishing between different compositions of members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series on a set of five representative samples, two from the upper suboxic and three from the lower sulfidic anoxic zone of gravity core GeoB 4901. Highly sensitive LT magnetic measurements were performed on magnetic extracts resulting in large differences in the magnetic behavior between samples from the different layers. This emphasizes that both Fe-Ti oxide phases occur in different proportions in the two geochemical environments. Most prominent are variations in the coercivity sensitive parameter coercive field (BC). At room-temperature (RT) hysteresis loops for all extracts are narrow and yield low coercivities (6-13 mT). With decreasing temperature the loops become more pronounced and wider. At 5 K an approximately 5-fold increase in BC for the suboxic samples contrasts a 20-25-fold increase for the samples from the anoxic zone. We demonstrate that this distinct increase in BC at LT corresponds to the increasing proportion of the Ti-rich hemoilmenite phase, while Fe-rich (titano-)magnetite dominates the magnetic signal at RT. This trend is also seen in the room-temperature saturation isothermal remanent magnetization (RT-SIRM) cycles: suboxic samples show remanence curves dominated by Fe-rich mineral phases while anoxic samples display curves clearly dominated by Ti-rich particles. We show that the EDS intensity ratios of the characteristic Fe Kalpha and Ti Kalpha lines of the Fe-Ti oxides may be used to differentiate between members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series. Furthermore it is possible to calculate an approximate composition for each grain if the intensity ratios of natural particles are linked to well-known standards. Thus, element spectra with high Fe/Ti intensity ratios were found to be rather typical of titanomagnetite while low Fe/Ti ratios are indicative of hemoilmenite. The EDS analyses confirm the LT magnetic results, Fe-rich magnetic phases dominate in the upper suboxic environment whereas Ti-rich magnetic phases comprise the majority of particles in the lower anoxic domain: The mineral assemblage of the upper suboxic environments is composed of magnetite (~19%), titanomagnetite (~62%), hemoilmenite (~17%) and ~2% other particles. In the lower anoxic sediments, reductive diagenetic alteration has resulted in more extensive depletion of the (titano-)magnetite phase, resulting in a relative enrichment of the hemoilmenite phase (~66%). In these strongly anoxic sediments stoichiometric magnetite is barely preserved and only ~5% titanomagnetite was detected. The remaining ~28% comprises Ti-rich particles such as pseudobrookite or rutile.

Magnesium/Calcium ratios and sea surface temperature estimation for sediments of the Timor Sea

We use a multiproxy approach to monitor changes in the vertical profile of the Indonesian Throughflow as well as monsoonal wind and precipitation patterns in the Timor Sea on glacial-interglacial, precessional, and suborbital timescales. We focus on an interval of extreme climate change and sea level variation: marine isotope (MIS) 6 to MIS 5e. Paleoproductivity fluctuations in the Timor Sea follow a precessional beat related to the intensity of the Australian (NW) monsoon. Paired Mg/Ca and d18O measurements of surface- and thermocline-dwelling planktonic foraminifers (G. ruber and P. obliquiloculata) indicate an increase of >4°C in both surface and thermocline water temperatures during Termination II. Tropical sea surface temperature changed synchronously with ice volume (benthic d18O) during deglaciation, implying a direct coupling of high- and low-latitude climate via atmospheric and/or upper ocean circulation. Substantial cooling and freshening of thermocline waters occurred toward the end of Termination II and during MIS 5e, indicating a change in the vertical profile of the Indonesian Throughflow from surface- to thermocline-dominated flow.

Benthic and planktic foraminiferal stable isotope records combined with Nd isotope ratios of ODP Hole 198-1210B

The Pacific Ocean is the largest water body on Earth, and circulation in the Pacific contributed significantly to climate evolution in the latest Cretaceous, the culmination of a period of long-term cooling. Here, we present new high-resolution late Campanian to Maastrichtian benthic and planktic foraminiferal stable isotope data and a neodymium (Nd) isotope record obtained from sedimentary ferromanganese oxide coatings of Ocean Drilling Program Hole 1210B from the tropical Pacific Ocean (Shatsky Rise). These new records resolve 13 million years in the latest Cretaceous, providing insights into changes in surface and bottom water temperatures and source regions of deep to intermediate waters covering the carbon isotope excursions of the Campanian-Maastrichtian Boundary Event (CMBE) and the Mid-Maastrichtian event (MME). Our new benthic foraminiferal d18O and Nd isotope records together with published Nd isotope data show markedly parallel trends across the studied interval over a broad range of bathyal to abyssal water depths interpreted to reflect changes in the intensity of deep-ocean circulation in the tropical Pacific. In particular, we observe a three-million-year-long period of cooler conditions in the early Maastrichtian (72.5 to 69.5 Ma) when a concomitant change toward less radiogenic seawater Nd isotope signatures probably marks a period of enhanced admixture and northward flow of deep waters with Southern Ocean provenance. We suggest this change to have been triggered by intensified formation and convection of deep waters in the high southern latitudes, a process that weakened during the MME (69.5 to 68.5 Ma). The early Maastrichtian cold interval is closely related to the negative and positive carbon isotope trends of the CMBE and MME. The millions-of-years long duration of these carbon cycle perturbations suggests a tectonic forcing of climatic cooling, possibly related to changes in ocean basin geometry and bathymetry.

(Table 2) Contents of chlorophyll a, organic carbon, nitrogen, and phosphorus and their molar ratios in dried matter of Ahnfeltia tobuchiensis agar containing seaweed from the Izmena Bay, Kunashir Island (South Kurils)

A complex study of influence of various environmental factors on rates of oxygen (M_O2 ), ammonium (M_NH4), and phosphate (M_PO4) metabolism in Ahnfeltia tobuchiensis has been carried out in situ in the Izmena Bay of the Kunashir Island. The following environmental factors have been included into the investigation: photosynthetically active radiation (PAR); ammonium (NH4); phosphate (PO4); and contents of carbon (C), nitrogen (N), phosphorus (P), and chlorophyll a (Chl) in tissue. Population of agar-containing seaweed A. tobuchiensis forms a layer with thickness up to 0.5 m, which occupies about 23.3 km**2; biomass is equal to 125000 tons. Quantitative assessment of organic matter production and nutrient consumption during oxygen metabolism has been carried out for the whole population. It has been shown that daily oxygen metabolism depends on PAR intensity, concentrations of PO4 and NH4 in seawater, and contents of N and P in tissues (r**2=0.78, p<0.001). Average daily NH4 consumption is 0.21 µmol/g of dry weight/hour and depends on NH4 and O2 concentrations in seawater and on ? and Chl a contents in algal tissues (r**2=0.64, p<0.001). Average daily PO4 consumption is 0.01 µmol/g of dry weight/hour and depends on NH4 concentrations in seawater and on P contents in algal tissues (r**2=0.40, p<0.001).

Sedimentology and Lead and Strontium isotope ratios of Miocene sediments from the Kerguelen Plateau

Characterization of sediment from Ocean Drilling Program Site 745, representing the East Kerguelen Ridge sediment drift, addresses important issues surrounding the timing of Miocene to present East Antarctic ice sheet stability and oceanic environmental change. Our results show three periods of greatly enhanced accumulation of Antarctic-derived sediment, at 6.4-5.9 Ma, 4.9-4.4 Ma and 1.1-0.8 Ma, potentially indicative of warmer, less stable ice sheets at these times. Conversely, the accumulation of Antarctic-derived material is comparatively less during the middle of the Pliocene warm epoch (4.8-3.2 Ma). The deep flow forming the Kerguelen drift was stronger during the latest Miocene and earliest Pliocene and has decreased in intensity continuously since then.

Paleomagnetic, stable oxygen isotope ratios, and U/Th activities of ODP Site 172-1062

Geomagnetic excursions are recognized as intrinsic features of the Earth's magnetic field. High-resolution records of field behaviour, captured in marine sedimentary cores, present an opportunity to determine the temporal and geometric character of the field during geomagnetic excursions and provide constraints on the mechanisms producing field variability. We present here the highest resolution record yet published of the Blake geomagnetic excursion (~125 ka) measured in three cores from Ocean Drilling Program (ODP) Site 1062 on the Blake-Bahama Outer Ridge. The Blake excursion has a controversial structure and timing but these cores have a sufficiently high sedimentation rate (~10cm/ka) to allow detailed reconstruction of the field behaviour at this site during the excursion. Palaeomagnetic measurements of the cores reveal rapid transitions (<500 yr) between the contemporary stable normal polarity and a completely reversed state of long duration which spans a stratigraphic interval of 0.7 m. We determine the duration of the reversed state during the Blake excursion using oxygen isotope stratigraphy, combined with 230Th excess measurements to assess variations in the sedimentation rates through the sections of interest. This provides an age and duration for the Blake excursion with greater accuracy and with constrained uncertainty. We date the directional excursion as falling between 129 and 122 ka with a duration for the deviation of 6.5±1.3 kyr. The long duration of this interval and the fully reversed field suggest the existence of a pseudo-stable, reversed dipole field component during the excursion and challenge the idea that excursions are always of short duration.

Separating ITCZ- and ENSO-related rainfall changes in the Galápagos over the last 3 kyr using D/H ratios of multiple lipid biomarkers

We present a 3000-yr rainfall reconstruction from the Galápagos Islands that is based on paired biomarker records from the sediment of El Junco Lake. Located in the eastern equatorial Pacific, the climate of the Galápagos Islands is governed by movements of the Intertropical Convergence Zone (ITCZ) and the El Niño-Southern Oscillation (ENSO). We use a novel method for reconstructing past ENSO- and ITCZ-related rainfall changes through analysis of molecular and isotopic biomarker records representing several types of plants and algae that grow under differing climatic conditions. We propose that ?D values of dinosterol, a sterol produced by dinoflagellates, record changes in mean rainfall in El Junco Lake, while dD values of C34 botryococcene, a hydrocarbon unique to the green alga Botryococcus braunii, record changes in rainfall associated with moderate-to-strong El Niño events. We use these proxies to infer changes in mean rainfall and El Niño-related rainfall over the past 3000 yr. During periods in which the inferred change in El Niño-related rainfall opposed the change in mean rainfall, we infer changes in the amount of ITCZ-related rainfall. Simulations with an idealized isotope hydrology model of El Junco Lake help illustrate the interpretation of these proxy reconstructions. Opposing changes in El Niño- and ITCZ-related rainfall appear to account for several of the largest inferred hydrologic changes in El Junco Lake. We propose that these reconstructions can be used to infer changes in frequency and/or intensity of El Niño events and changes in the position of the ITCZ in the eastern equatorial Pacific over the past 3000 yr. Comparison with El Junco Lake sediment grain size records indicates general agreement of inferred rainfall changes over the late Holocene.

Delta 66Zn ratios and age of carbonates from ODP Site 138-849 (Table 1)

The carbonate fraction of sediment core ODP 849, leg 138, located in the eastern equatorial Pacific, mostly consisting of coccoliths, was separated and analyzed for its Zn isotopic composition. The overall variation in Zn isotopic composition, as determined by multiple-collector, magnetic-sector, inductively coupled plasma mass spectrometry, was found to be on the order of 1? (expressed in delta66Zn, where deltaxZn=[(xZn/64Zn)sample/(xZn/64Zn)standard -1]*10**3 and x=66, 67 or 68) over the last 175 ka. The analytical precision was 0.04 per mil and the overall reproducibility was usually better than 0.07 per mil. The Zn isotopic composition signal exhibits several marked peaks and a high-frequency variability. A periodogram of the delta66Zn signal showed two periodicities of 35.2 and 21.2 ka. We suggest that the latter is caused by the precession of the Earth's axis of rotation. The periodogram exhibits a minimum at 41.1 ka, thus showing that the Zn isotopic composition is independent of the obliquity in the eastern equatorial Pacific. The range of delta66Zn values observed for the carbonate fraction of ODP 849 overlaps with the range observed for Fe-Mn nodules in the world's oceans, which suggests that seawater/carbonate Zn isotope fractionation is weak. We therefore assume that most of the Zn isotope variability is a result of the selective entrainment of the light isotopes by organic matter in the surface ocean. The ODP 849 delta66Zn record seems to follow the changes in the insolation cycles. Changes in the late summer/fall equatorial insolation modulate the intensity of the equatorial upwelling, hence the mixing between deep and surface waters. We propose that during decreased summer/fall equatorial insolation, when a steep thermocline can develop (El Niño-like conditions), the surface waters cannot be replenished by deep waters and become depleted in the lighter Zn isotopes by biological activity, thus resulting in the progressive increase of the delta66Zn values of the carbonate shells presumably in equilibrium with surface seawater.

Pore water isotopic ratios of CO2 and SO4, and sediment CH4 content of ODP Leg 164 sites

A unique set of geochemical pore-water data, characterizing the sulfate reduction and uppermost methanogenic zones, has been collected at the Blake Ridge (offshore southeastern North America) from Ocean Drilling Program (ODP) Leg 164 cores and piston cores. The d13C values of dissolved CO2 (sum CO2) are as 13C-depleted as -37.7 per mil PDB (Site 995) at the sulfate-methane interface, reflecting a substantial contribution of isotopically light carbon from methane. Although the geochemical system is complex and difficult to fully quantify, we use two methods to constrain and illustrate the intensity of anaerobic methane oxidation in Blake Ridge sediments. An estimate using a two-component mixing model suggests that ~24% of the carbon residing in the sum CO2 pool is derived from biogenic methane. Independent diagenetic modeling of a methane concentration profile (Site 995) indicates that peak methane oxidation rates approach 0.005 µmol/cm**3/yr, and that anaerobic methane oxidation is responsible for consuming ~35% of the total sulfate flux into the sediments. Thus, anaerobic methane oxidation is a significant biogeochemical sink for sulfate, and must affect interstitial sulfate concentrations and sulfate gradients. Such high proportions of sulfate depletion because of anaerobic methane oxidation are largely undocumented in continental rise sediments with overlying oxic bottom waters. We infer that the additional amount of sulfate depleted through anaerobic methane oxidation, fueled by methane flux from below, causes steeper sulfate gradients above methane-rich sediments. Similar pore water chemistries should occur at other methane-rich, continental-rise settings associated with gas hydrates.

Stable isotope ratios of planktonic foraminifera from the West Equatorial Pacific

Differential dissolution affects the isotopic composition of different species of planktonic foraminifera in different ways. In the two species studied here in cores from Ontong Java Plateau, the less resistant species, Globigerinoides sacculifer, is more readily affected at a shallower depth than the more resistant species, Pulleniatina obliquiloculata (2.9 versus 3.4 km), but shows a smaller and less predictable response to partial dissolution (0.2 to 0.3 per mil versus 0.6 to 0.7 per mil). Comparison of isotopic values from the last glacial period with those from the late Holocene indicates that the apparent dissolution effect is considerably reduced during the last glacial, presumably due to reduced dissolution intensity during glacial time. A change in the level of the lysocline of about 400 m is suggested. In the published isotope records from Pacific cores V28-238 and V28-239, the dissolution-generated difference in delta18O (noted previously by Shackleton and Opdyke [1976]) is seen to describe a mid-Brunhes dissolution maximum, between 300 and 500 thousand years ago. This mid-Brunhes dissolution excursion is well known from the Pacific and the Indian Ocean.