Low-temperature experiments of sediment core GeoB6229-6 at the South American continental margin off the Rio de la Plata estuary

With various low-temperature experiments performed on magnetic mineral extracts of marine sedimentary deposits from the Argentine continental slope near the Rio de la Plata estuary, a so far unreported style of partial magnetic self-reversal has been detected. In these sediments the sulphate-methane transition (SMT) zone is situated at depths between 4 and 8 m, where reductive diagenesis severely alters the magnetic mineral assemblage. Throughout the sediment column magnetite and ilmenite are present together with titanomagnetite and titanohematite of varying compositions. In the SMT zone (titano-)magnetite only occurs as inclusions in a siliceous matrix and as intergrowths with lamellar ilmenite and titanium-rich titanohematite, originating from high temperature deuteric oxidation within the volcanic host rocks. These abundant structures were visualized by scanning electron microscopy and analysed by energy dispersive spectroscopy. Warming of field-cooled and zero-field-cooled low-temperature saturation remanence displays magnetic phase transitions of titanium-rich titanohematite below 50 K and the Verwey transition of magnetite. A prominent irreversible decline characterizes zero-field cooling of room temperature saturation remanence. It typically sets out at ~210 K and is most clearly developed in the lower part of the SMT zone, where low-temperature hysteresis measurements identified ~210 K as the blocking temperature range of a titanohematite phase with a Curie temperature of around 240 K. The mechanism responsible for the marked loss of remanence is, therefore, sought in partial magnetic self-reversal by magnetostatic interaction of (titano-)magnetite and titanohematite. When titanohematite becomes ferrimagnetic upon cooling, its spontaneous magnetic moments order antiparallel to the (titano-)magnetite remanence causing an drastic initial decrease of global magnetization. The loss of remanence during subsequent further cooling appears to result from two combined effects (1) magnetic interaction between the two phases by which the (titano-)magnetite domain structure is substantially modified and (2) low-temperature demagnetization of (titano-)magnetite due to decreasing magnetocrystalline anisotropy. The depletion of titanomagnetite and superior preservation of titanohematite is characteristic for strongly reducing sedimentary environments. Typical residuals of magnetic mineral assemblages derived from basaltic volcanics will be intergrowths of titanohematite lamellae with titanomagnetite relics. Low-temperature remanence cycling is, therefore, proposed as a diagnostic method to magnetically characterize such alteration (palaeo-)environments.

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.

Preliminary results and documentation of sediment cores CRP2 and CRP-2A from the Ross Sea off Cape Roberts, Antarctica

The site for CRP-2, 14 km east of Cape Roberts (77.006°S; 163.719°E), was selected to overlap the early Miocene strata cored in nearby CRP-1, and to sample deeper into the east-dipping strata near the western margin ofe he Victoria Land Basin to investigate Palaeogene climatic and tectonic history. CRP-2 was cored from 5 to 57 mbsf (metres below the sea floor) (core recovery 91 %), with a deviation resulting in CRP-2A being cored at the same site. CRP-2A reached down to 624mbsf (recovery 95%), and to strata with an age of c. 33-35 Ma. Drilling took place from 16 October to 25 November 1998, on 2.0-2.2 m of sea ice and through 178 m of water. Core fractures and other physical properties, such as sonic velocity, density and magnetic susceptibility, were measured throughout the core. Down-hole logs for these and other properties were run from 63 to 167 mbsf and subsequently from 200 to 623 mbsf, although density and velocity data could be obtained only to 440 mbsf because of hole collapse. Sonic velocity averages c. 2.0 km S-1 for the upper part of the hole, but there is an sharp increase to c. 3.0 km s-1 and also a slight angular unconformity, at 306 mbsf, corresponding most likely to the early/late Oligocene boundary (c. 28-30 Ma). Velocity then increases irregularly to around 3.6 km s-1 at the bottom of the hole, which is estimated to lie 120 m above the V4/V5 boundary. The higher velocities below 306 mbsf probably reflect more extensive carbonate and common pyrite cementation, in patches, nodules, bedding-parallel masses and as vein infills. Dip of the strata also increases down-hole from 3° in the upper 300 in to over 10° at the bottom. Temperature gradient is 21° k-1. Over 2 000 fractures were logged through the hole. Borehole televiewer imagery was obtained for the interval from 200 to 440 mbsf to orient the fractures for stress field analysis. Lithostratigraphical descriptions on a scale of 1:20 are presented for the full length of the core, along with core box images, as a 200 page supplement to this issue. The hole initially passed through a layer of muddy gravel to 5.5 mbsf (Lithological Sub-Unit or LSU 1.1), and then into a Quaternary diatom-bearing clast-rich diamicton to 21 mbsf (LSU 2. l), with an interval of alternating compact diamicton and loose sand, and containing a rich Pliocene foraminiferal fauna, to 27 mbsf (LSU 2.2). The unit beneath this (LSU 3.1) has similar physical properties (sonic velocity, porosity, magnetic susceptibility) and includes diamictites of similar character to those of LSU 2.1 and 2.2, but an early Miocene (c. 19 Ma) diatom assemblage at 28 mbsf (top of LSU 3.1) shows that this sub-unit is part of the older section. The strata beneath 27 mbsf, primary target for the project, extend from early Miocene to perhaps latest Eocene age, and are largely cyclic glacimarine nearshore to offshore sediments. They are described as 41 lithological sub-units and interpreted in terms of 12 recurrent lithofacies. These are 1) mudstone, 2) inter-stratified mudstone and sandstone, 3) muddy very fine to coarse sandstone, 4) well-sorted stratified fine sandstone, 5) moderately to well-sorted, medium-grained sandstone, 6) stratified diamictite, 7) massive diamictite, 8) rhythmically inter-stratified sandstone and mudstone, 9) clast-supported conglomerate, 10) matrix-supported conglomerate, 11) mudstone breccia and 12) volcaniclastic sediment. Sequence stratigraphical analysis has identified 22 unconformity-bounded depositional sequences in pre- Pliocene strata. They typically comprise a four-part architecture involving, in ascending order, 1) a sharp-based coarse-grained unit (Facies 6,7,9 or 10), 2) a fining-upward succession of sandstones (Facies 3 and 4), 3) a mudstone interval (Facies l), in some cases coarsening upward to muddy sandstones (Facies 3), and 4) a sharp-based sandstone dominated succession (mainly Facies 4). The cyclicity recorded by the strata is interpreted in terms of a glacier ice margin retreating and advancing from land to the west, and of rises and falls in sea level. Analysis of sequence periodicity awaits afirmer chronology. However, apreliminary spectral analysis of magnetic susceptibility for a deepwater mudstone within one of the sequences (from 339 to 347 mbsf) reveals ratios between hierarchical levels that are similar to those of the three Milankovitch orbital forcing periodicities. The strata contain a wide range of fossils, the most abundant being marine diatoms. These commonly form up to 5% of the sediment, though in places the core is barren (notably between 300 and 412 mbsf). Fifty samples out of 250 reviewed were studied in detail. The assemblages define ten biostratigraphical zones, some of them based on local or as yet undescribed forms. The assemblages are neritic, and largely planktonic, suggesting that the sea floor was mostly below the photic zone throughout deposition of the corcd sequence. Calcareous nannofossils, representing incursions of ocean surface waters, are much less common (72 out of 183 samples examined) and restricted to mudstone intervals a few tens of metres thick, but are important for dating. Foraminifera are also sparse (73 out of 135 samples) and represented only by calcareous benthic species. Changing assemblages indicate a shift from inshore environments in the early Oligocenc to outer shelf in the late Oligocenc, returning to inshore in the early Miocene. Marine palynomorplis yielded large numbers of well-preserved forms from most of the 116 samples examined. The new in situ assemblagc found last year in CRP-1 is extended down into the late Oligocene and a further new assemblage is found in the early Oligoccnc. Many taxa are new, and cannot us yet contribute to an improved understanding of chronology or ecology. Marine invertebrate macrofossils, mostly molluscs and serpulid tubes, are scattered throughout the core. Preservation is good in mudstones but poor in other lithologies. Climate on land is reflected in the content of terrestrial palynomorphs, which are extremely scarce down to c. 300 mbsf. Some forms are reworked, and others represent a low growing sparse tundra with at least one species of Nothofagus. Beneath this level, a significantly greater diversity and abundance suggests a milder climate and a low diversity woody vegetation in the early Oligocene, but still far short of the richness found in known Eocene strata of the region. Sedimentary facies in the oldest strata also suggest a milder climate in the oldest strata cored, with indications of substantial glacial melt-water discharges, but are typical of a coldcr climate in late Oligocene and early Miocene times. Clast analyses from diamictites reveal weak to random fabrics, suggesting either lack of ice-contact deposition or post-depositional modification, but periods when ice grounded at the drill site are inferred from thin zones of in-situ brecciated rock and soft-sediment folding. These are more common above c. 300 mbsf, perhaps reflecting more extensive glacial advances during deposition of those strata. Erosion of the adjacent Transantarctic Mountains through Jurassic basalt and dolerite-intruded Beacon strata into basement rocks beneath is recorded by petrographical studies of clast and sand grain assemblages. Core below 310 mbsf contains a dominance of fine-grained Jurassic dolerite and basalt fragments along with Beacon-derived coal debris and rounded quartz grains, whereas the strata above this level have a much higher proportion of basement derived granitoids, implying that the large areas of the adjacent mountains had been eroded to basement by the end of the early Oligocene. There is little indication of rift-related volcanism below 310 mbsf. Above this, however, basaltic and trachytic tephras are common, especially from 280 to 200 mbsf, from 150 to 46 mbsf, and in Pliocene LSU 2.2 from 21 to 27 mbsf. The largest volcanic eruptions generated layers of coarse (up to 1 cm) trachytic pumice lapilli between 97 and 114 mbsf. The thickest of these (1.2 m at 112 mbsf) may have produced an eruptive column extending tens of km into the stratosphere. A source within a few tens of km of the drill site is considered most likely. Present age estimates for the pre-Pliocene sequence are based mainly on biostratigraphy (using mainly marine diatoms and to a lesser extent calcareous nannofossils), with the age of the tephra from 112 to 114 mbsf (21.44k0.05 Ma from 84 crystals by Ar-Ar) as a key reference point. Although there are varied and well-preserved microfossil assemblages through most of the sequence (notably of diatoms and marine palynomorphs), they comprise largely taxa either known only locally or as yet undescribed. In addition, sequence stratigraphical analysis and features in the core itself indicate numerous disconformities. The present estimate from diatom assemblages is that the interval from 27 to 130 mbsf is early Miocene in age (c. 19 to 23.5 Ma), consistent with the Ar-Ar age from 112 to 114 mbsf. Diatom assemblages also indicate that the late Oligocene epoch extends from c. 130 to 307 mbsf, which is supported by late Oligocene nannofossils from 130 to 185 mbsf. Strata from 307 to 412 mbsf have no age-diagnostic assemblages, but below this early Oligocene diatoms and nannofossils have been recovered. A nannoflora at the bottom of the hole is consistent with an earliest Oligocene or latest Eocene age. Magnetostratigraphical studies based on about 1000 samples, 700 of which have so far undergone demagnetisation treatment, have provided a polarity stratigraphy of 12 pre-Pliocene magnetozones. Samples above 270 mbsf are of consistently high quality. Below this, magnetic behaviour is more variable. A preliminary age-depth plot using the Magnetic Polarity Time Scale (MPTS) and constrained by biostratigraphical data suggests that episodes of relatively rapid sedimentation took place at CRP-2 during Oligocene times (c. 100 m/My), but that more than half of the record was lost in a few major and many minor disconformities. Age estimates from Sr isotopes in shell debris and further tephra dating are expected to lead to a better comparison with the MPTS. CRP-2/2A has recorded a history of subsidence of the Victoria Land Basin margin that is similar to that found in CIROS-170 km to the south, reflecting stability in both basin and the adjacent mountains in late Cenozoic times, but with slow net accumulation in the middle Cenozoic. The climatic indicators from both drill holes show a similar correspondence, indicating polar conditions for the Quaternary but with sub-polar conditions in the early Miocene-late Oligocene and indications of warmer conditions still in the early Oligocene. Correlation between the CRP-2A core and seismic records shows that seismic units V3 and V4, both widespread in the Victoria Land Basin, represent a period of fluctuating ice margins and glacimarine sedimentation. The next drill hole, CRP-3, is expected to core deep into V5 and extend this record of climate and tectonics still further back in time.

Mg/Ca-temperature proxy in benthic foraminifera from the Florida Strait

Over the past decade, the ratio of Mg to Ca in foraminiferal tests has emerged as a valuable paleotemperature proxy. However, large uncertainties remain in the relationships between benthic foraminiferal Mg/Ca and temperature. Mg/Ca was measured in benthic foraminifera from 31 high-quality multicore tops collected in the Florida Straits, spanning a temperature range of 5.8° to 18.6°C. New calibrations are presented for Uvigerina peregrina, Planulina ariminensis, Planulina foveolata, and Hoeglundina elegans. The Mg/Ca values and temperature sensitivities vary among species, but all species exhibit a positive correlation that decreases in slope at higher temperatures. The decrease in the sensitivity of Mg/Ca to temperature may potentially be explained by Mg/Ca suppression at high carbonate ion concentrations. It is suggested that a carbonate ion influence on Mg/Ca may be adjusted for by dividing Mg/Ca by Li/Ca. The Mg/Li ratio displays stronger correlations to temperature, with up to 90% of variance explained, than Mg/Ca alone. These new calibrations are tested on several Last Glacial Maximum (LGM) samples from the Florida Straits. LGM temperatures reconstructed from Mg/Ca and Mg/Li are generally more scattered than core top measurements and may be contaminated by high-Mg overgrowths. The potential for Mg/Ca and Mg/Li as temperature proxies warrants further testing.

Homogenization of Portuguese long-term temperature data series: Lisbon, Coimbra and Porto

Three long-term temperature data series measured in Portugal were studied to detect and correct non-climatic homogeneity breaks and are now available for future studies of climate variability. Series of monthly minimum (Tmin) and maximum (Tmax) temperatures measured in the three Portuguese meteorological stations of Lisbon (from 1856 to 2008), Coimbra (from 1865 to 2005) and Porto (from 1888 to 2001) were studied to detect and correct non-climatic homogeneity breaks. These series together with monthly series of average temperature (Taver) and temperature range (DTR) derived from them were tested in order to detect homogeneity breaks, using, firstly, metadata, secondly, a visual analysis and, thirdly, four widely used homogeneity tests: von Neumann ratio test, Buishand test, standard normal homogeneity test and Pettitt test. The homogeneity tests were used in absolute (using temperature series themselves) and relative (using sea-surface temperature anomalies series obtained from HadISST2 close to the Portuguese coast or already corrected temperature series as reference series) modes. We considered the Tmin, Tmax and DTR series as most informative for the detection of homogeneity breaks due to the fact that Tmin and Tmax could respond differently to changes in position of a thermometer or other changes in the instrument's environment; Taver series have been used, mainly, as control. The homogeneity tests show strong inhomogeneity of the original data series, which could have both internal climatic and non-climatic origins. Homogeneity breaks which have been identified by the last three mentioned homogeneity tests were compared with available metadata containing data, such as instrument changes, changes in station location and environment, observing procedures, etc. Significant homogeneity breaks (significance 95% or more) that coincide with known dates of instrumental changes have been corrected using standard procedures. It was also noted that some significant homogeneity breaks, which could not be connected to the known dates of any changes in the park of instruments or stations location and environment, could be caused by large volcanic eruptions. The corrected series were again tested for homogeneity: the corrected series were considered free of non-climatic breaks when the tests of most of monthly series showed no significant (significance 95% or more) homogeneity breaks that coincide with dates of known instrument changes. Corrected series are now available in the frame of ERA-CLIM FP7 project for future studies of climate variability.

Temperature affects the morphology and calcification of Emiliania huxleyi strains

The global warming debate has sparked an unprecedented interest in temperature effects on coccolithophores. The calcification response to temperature changes reported in the literature, however, is ambiguous. The two main sources of this ambiguity are putatively differences in experimental setup and strain-specificity. In this study we therefore compare three strains isolated in the North Pacific under identical experimental conditions. Three strains of Emiliania huxleyi type A were grown under non-limiting nutrient and light conditions, at 10, 15, 20 and 25 ºC. All three strains displayed similar growth rate versus temperature relationships, with an optimum at 20-25 ºC. Elemental production (particulate inorganic carbon (PIC), particulate organic carbon (POC), total particulate nitrogen (TPN)), coccolith mass, coccolith size, and width of the tube elements cycle were positively correlated with temperature over the sub-optimum to optimum temperature range. The correlation between PIC production and coccolith mass/size supports the notion that coccolith mass can be used as a proxy for PIC production in sediment samples. Increasing PIC production was significantly positively correlated with the percentage of incomplete coccoliths in one strain only. Generally, coccoliths were heavier when PIC production was higher. This shows that incompleteness of coccoliths is not due to time shortage at high PIC production. Sub-optimal growth temperatures lead to an increase in the percentage of malformed coccoliths in a strain-specific fashion. Since in total only six strains have been tested thus far, it is presently difficult to say whether sub-optimal temperature is an important factor causing malformations in the field. The most important parameter in biogeochemical terms, the PIC:POC, shows a minimum at optimum growth temperature in all investigated strains. This clarifies the ambiguous picture featuring in the literature, i.e. discrepancies between PIC:POC-temperature relationships reported in different studies using different strains and different experimental setups. In summary, global warming might cause a decline in coccolithophore's PIC contribution to the rain ratio, as well as improved fitness in some genotypes due to less coccolith malformations.

Geochemistry and sedimentation rates of ODP Leg 199 sites and of surface sediments in the eastern Pacific ocean

We present the first high-resolution organic carbon mass accumulation rate (MAR) data set for the Eocene equatorial Pacific upwelling region, from Sites 1218 and 1219 of the Ocean Drilling Program. A maximum Corg MAR anomaly appears at 41 Ma and corresponds to a high carbonate accumulation event (CAE). Independent evidence suggests that this event (CAE-3) was a time of rapid cooling. Throughout the Eocene, organic carbon burial fluxes were an order of magnitude lower than fluxes recorded for the Holocene. In contrast, the expected organic carbon flux, calculated from the biogenic barium concentrations for these sites, is roughly equal to modern. A sedimentation anomaly appears at 41 Ma, when both the measured and the expected organic carbon MAR increases by a factor of two-three relative to the background Eocene fluxes. The rain of estimated Corg and barium from the euphotic zone to the sediments increased by factors of three and six, respectively. We suggest that the discrepancy between the expected and measured Corg in the sediments is a direct consequence of the increased metabolic rates of all organisms throughout the Eocene oceans and sediments. This hypothesis is supported by recent work in ecology and biochemical kinetics that recognizes the fundamental basis of ecology as following from the laws of thermodynamics. This dependence is now elucidated as the Universal Temperature Dependence (UTD) "law" of metabolism and can be applied to all organisms over their biologically relevant temperature range. The general pattern of organic carbon and barium deposition throughout the Eocene is consistent with the UTD theory. In particular, the anomaly at 41 Ma (CAE-3) is associated with rapid cooling, an event that triggered slower metabolic rates for all organisms, slower recycling of organic carbon in the water and sediment column, and, consequently, higher deposition of organic carbon in the sediments. This "metabolism-based" scenario is consistent with the sedimentation patterns we observe for both Sites 1218 and 1219.

Sea-surface temperature reconstructions for the Quaternary western Atlantic

Paleotemperature estimates calculated by the SIMMAX Modern Analog Technique are presented for two gravity cores from the Rio Grande Rise, one from the Brazil Slope, and one from the Ceara Rise. The estimates are based on comparisons between modern and fossil planktonic foraminiferal assemblages and were carried out on samples from Quaternary sediments. Estimated warm-season temperatures from the Rio Grande Rise (at approx. 30° S) range from around 19°C to 24°C, with some coincidence of warm peaks with interglacial stages. The temperature estimates (also warm-season) from the more tropical Brazil Slope (at approx. 8° S) and Ceara Rise (at approx. 4° N) cores are more stable, remaining between 26°C and 28°C throughout most of their lengths. This fairly stable situation in the tropical western Atlantic is interrupted in oxygen isotope stage 6 by a significant drop of 2-3°C in both of these cores. Temperature estimates from the uppermost samples in all cores compare very well to the modern-day measured values. Affinities of some foraminiferal species for warmer or cooler surface temperatures are identified within the temperature range of the examined samples based on their abundance values. Especially notable among the warmer species are, Globorotalia menardii, Globigerinita glutinata, Globigerinoides ruber, and Globigerinoides sacculifer. Species indicative of cooler surface temperatures include Globorotalia inflata, Globigerina bulloides, Neogloboquadrina pachyderma, and Globigerina falconensis. A cluster analysis was carried out to assist in understanding the degree of variation which occurs in the foraminiferal assemblages, and how temperature differences influence the faunal compositions of the samples. It is demonstrated that fairly similar samples may have unexpectedly different estimated temperatures due to small differences in key species and, conversely, quite different assemblages can result in similar or identical temperature estimates which confirms that other parameters than just temperature affect faunal content.