Cenozoic magnetostratigraphy of ODP holes 113-689B and 113-690B

A detailed paleomagnetic study was carried out on biosiliceous and calcareous sediments drilled on Maud Rise, Antarctica, during ODP Leg 113. High-quality APC sections were retrieved in the upper 220 m of Holes 689B and 690B. Average deposition rates range from 3 to 15 m/m.y. A close (25 cm) paleomagnetic sample spacing provided a medium-resolution magnetostratigraphic sequence for the Paleogene and Neogene. Paleomagnetic samples were demagnetized stepwise by alternating fields, and characteristic remanent magnetization directions were derived from detailed vector and difference vector component analysis. A magnetochronologic framework has been established for the first time for the Southern Ocean sedimentary sequences spanning Paleocene to Oligocene and middle Miocene to early Pliocene times. Biosiliceous and calcareous microfossil stratigraphies were used to constrain magnetostratigraphic age assignments. Although average sedimentation rates were rather low, nearly complete sections of the geomagnetic polarity time scale (e.g., Chrons C5 and C5A) could be correlated with the inferred polarity pattern. Miocene and Pliocene records are marked by a high number of hiatuses mainly identified by diatom biostratigraphy. Good paleomagnetic correlation between the two holes is afforded in particular in the middle to upper Miocene. Oligocene magnetostratigraphy reveals a high-quality paleomagnetic record with a mostly complete Oligocene section in Hole 689B at ~5 m/m.y. deposition rate. Hole 690B exhibits higher deposition rates (7-12 m/m.y.), although two hiatuses are present. Early and late Eocene sedimentary sequences could be analyzed in both holes, but in Hole 689B middle Eocene chrons were disrupted by hiatuses and only incomplete polarity intervals C21 and C24 were encountered. Highest resolution (14 m/m.y.) was achieved in Hole 690B in a complete early Eocene and late Paleocene sequence from Chrons C23 to C26, with a number of short polarity intervals detected within Chrons C24 and C25.

Magnetic properties of ODP Hole 116-717C

Dark gray and black mud turbidites cored on ODP Leg 116 commonly yielded large magnetic susceptibility peaks. What is more, these peaks displayed different shapes suggesting variations in sedimentological processes. Consequently, a detailed study of the magnetic properties of two of these turbidites was undertaken to better understand the source of their unusual magnetism. Physical properties were measured as was the demagnetization behavior of sample natural remanent magnetizations (NRMs). Subsequently, an anhysteretic remanent magnetization (ARM) and saturation isothermal remanent magnetization (SIRM) were imparted to the samples, demagnetized, and various grain size tests based on the behavior of these remanences were applied. Finally, magnetic concentrates from two samples were examined with a scanning electron microscope with the capability to do energy dispersive X-ray (EDX) analysis. The turbidites stand out from surrounding layers because of their high susceptibilities, NRMs, ARMs, SIRMs, and ratios of ARM and SIRM to susceptibility. Their alternating field and thermal demagnetization properties and IRM acquisition curves are consistent with titanomagnetite grains as the primary magnetic mineral with some amount of hematite present. These properties are very similar to those published for samples from the Deccan flood basalts and suggest this formation as a possible source of the magnetic grains. Magnetic granulometry tests implied that the magnetic particles behave dominantly as single-domain and pseudo-single-domain grains. Moreover, they also implied that the large variation in susceptibility observed in the black mud turbidites results from a tenfold increase in the concentration of titanomagnetite grains. Electron microscope, EDX, and SIRM analyses revealed detrital titanomagnetites with typical sizes around 8-10 µm, but as large as 20-25 µm. These are probably the dominant magnetic grains in the black mud turbidites; however, ARM and susceptibility frequency-dependence suggested that there may also be a submicrometer fraction present. Most of the observed titanomagnetite grains are tabular and some display exsolution lamellae, accounting for the pseudo-single-domain behavior despite their moderate sizes. We hypothesize that the magnetic mineral concentration variations are brought about by sedimentological factors. The heavier magnetic minerals may tend to sink to the bottom of a turbidite; however, sometimes turbidite turbulence may act to keep these tabular, medium-size grains in suspension longer than some other larger or more equidimensional grains. Consequently, the susceptibility peak shape may reflect the turbidite current velocities as well as other sedimentological factors.

Paleomagnetic measurements of 10 sediment profiles from the Antarctic continental slope

Die im Rahmen des zweijährigen Forschungsprojekts über paläomagnetisch-sedimentologische Analysen sedimentärer Zyklen in der Weddell See und ihre stratigraphische Interpretation durchgeführten Arbeiten lieferten Ergebnisse zur Geschichte glaziomariner Sedimentationsprozesse am antarktischen Kontinentalrand. So konnte für ein Kernprofil mit einer außergewöhnlichen Terassenstruktur eine fazielle Gliederung und stratigraphische Einordnung erreicht werden, die auch auf größere Areale in der Weddell See anwendbar sind. Aufgrund der stratigraphischen Randbedingungen konnten die gewonnenen paläo- und gesteinsmagnetischen Messungen in eine Altersstruktur integriert und zusammen mit den sedimentologischen Parametern im Hinblick auf lokale und regionale Umweltveränderungen interpretiert werden. Insbesondere die gesteinsmagnetischen Analysen haben gezeigt, daß die magnetische Kornfraktion als accessorischer Bestandteil im Gesamtsediment dennoch an die Sortierungsprozesse des terrigenen Sedimenteintrags gekoppelt ist. Die ungewöhnlich deutlichen Variationen korngrößenabhängiger Parameter zeigten weiterhin, daß in Verbindung mit einer hochauflösenden Stratigraphie die magnetische Detailanalyse und ein besseres Verständnis der Sedimentationsprozesse in der Nähe der Schelfeiskante und speziell bei Meeresspiegeltiefständen die Möglichkeit eröffnen, unmittelbar Aussagen über die Bewegungen der Schelfeise und die Qualität der Meereisbedeckungen zu machen. Die gezielte Fortsetzung dieser Arbeiten in anderen Arealen am antarktischen Kontinentalrand ist daher wünschenswert. Die verwendeten Verfahren lassen sich mit den derzeit verfügbaren Instrumenten noch erweitern und versprechen durch die sehr sensitive Methodik detaillierte Aussagen zu glaziomarinen Sedimentationsprozessen.

Paleomagnetic and stable isotope measurements and distribution of benthic foraminifera in sediment core PS1388-3 from the Antarctic continental margin in the eastern Weddell Sea

A stable isotope record from the eastern Weddell Sea from 69°S is presented. For the first time, a 250,000-yr record from the Southern Ocean can be correlated in detail to the global isotope stratigraphy. Together with magnetostratigraphic, sedimentological and micropalaeontological data, the stratigraphic control of this record can be extended back to 910,000 yrs B.P. A time scale is constructed by linear interpolation between confirmed stratigraphic data points. The benthic d18O record (Epistominella exigua) reflects global continental ice volume changes during the Brunhes and late Matuyama chrons, whereas the planktonic isotopic record (Neogloboquadrina pachyderma) may be influenced by a meltwater lid caused by the nearby Antarctic ice shelf and icebergs. The worldwide climatic improvement during deglaciations is documented in the eastern Weddell Sea by an increase in production of siliceous plankton followed, with a time lag of approximately 10,000 yrs, by planktonic foraminifera production. Peak values in the difference between planktonic and benthic d13C records, which are 0.5 per mil higher during warm climatic periods than during times with expanded continental ice sheets, also suggest increased surface productivity during interglacials in the Southern Ocean.

Sedimentological and paleomagnetic investigations on two gravity cores and ODP sites 113-690 and 693 off Kapp Norvegia, Antarctic continental margin

Oligocene to Quaternary sediments were recovered from the Antarctic continental margin in the eastern Weddell Sea during ODP Leg 113 and Polarstern expedition ANT-VI. Clay mineral composition and grain size distribution patterns are useful for distinguishing sediments that have been transported by ocean currents from those that were ice-rafted. This, in turn, has assisted in providing insights about the changing late Paleogene to Neogene sedimentary environment as the cryosphere developed in Antarctica. During the middle Oligocene, increasing glacial conditions on the continent are indicated by the presence of glauconite sands, that are interpreted to have formed on the shelf and then transported down the continental slope by advancing glaciers or as a result of sea-level lowering. The dominance of illite and a relatively high content of chlorite suggest predominantly physical weathering conditions on the continent. The high content of biogenic opal from the late Miocene to the late Pliocene resulted from increased upwelling processes at the continental margin due to increased wind strength related to global cooling. Partial melting of the ice-sheet occurred during an early Pliocene climate optimum as is shown by an increasing supply of predominantly current-derived sediment with a low mean grain size and peak values of smectite. Primary productivity decreased at ~ 3 Ma due to the development of a permanent sea-ice cover close to the continent. Late Pleistocene sediments are characterized by planktonic foraminifers and biogenic opal, concentrated in distinct horizons reflecting climatic cycles. Isotopic analysis of AT. pachyderma produced a stratigraphy which resulted in a calculated sedimentation rate of 1 cm/k.y. during the Pleistocene. Primary productivity was highest during the last three interglacial maxima and decreased during glacial episodes as a result of increasing sea-ice coverage.

Oligocene magnetostratigraphy for equatorial Pacific ODP Sites

An Oligocene magnetostratigraphy from ODP Sites 1218 and 1219 (Equatorial Pacific) has been obtained by measurements made on u-channel samples, augmented by about 221 discrete samples. U-channel samples were measured at 1 cm intervals and were stepwise demagnetized in alternating fields (AF) up to a maximum peak field of 80 mT. The magnetization directions were determined at 1 cm intervals by principal component analysis of demagnetization steps in the 20 to 60 mT peak field range. A similar treatment was carried out on the discrete samples, which confirmed the results obtained with u-channel measurements. Sites 1218 and 1219 were precisely correlated based on multisensor track, paleontological and shipboard magnetostratigraphic data; this correlation is substantiated by u-channel measurements. Although the magnetostratigraphy obtained from the u-channels is similar to the interpretation deduced from shipboard measurements based on blanket demagnetization at peak AF of 20 mT, the u-channel results are substantially more robust since many interpretative uncertainties are resolved by the stepwise demagnetization and higher stratigraphic resolution. The temporal resolution of u-channel-based magnetic stratigraphy in the Oligocene section of Sites 1218 and 1219 is better than 5 kyr, and it is therefore suitable for detection of brief polarity subchrons. However, in spite of the high resolution, we did not find any reversals corresponding to the numerous cryptochrons identified in this time span by Cande and Kent (1995, doi:10.1029/94JB03098).

Magnetic properties of basalts and sediments of ODP Leg 135 sites

Paleomagnetic and rock-magnetic investigations of basalts from Hole 834B in the Lau backarc basin and of sediments from Holes 841A and 841B at the Tonga Ridge are reported. Three groups of blocking temperatures in the basalts suggest the presence of at least three magnetic phases: pure magnetite, a Ti-poor titanomagnetite, and a Ti-rich phase. The drill-string-induced remanence in the basalts is typically between three and six times the original normal remanent magnetization intensity, but it is mostly removed by alternating-field (AF) cleaning in 5 mT. Volume susceptibility values range from 0.04 * 10**-3 to 4 * 10**-3 cgs. The modified Q-ratio J5/sus ranges from 0.5 to 10. The drill-string-induced remanence behaves different in the two sediment cores from Holes 841A and 841B, which may be the result of differences in the sediment or caused by the different drilling equipment used. The AF-cleaned inclinations of the sediment in Holes 841A and 841B suggest a slight flattening with increasing depth (up to 6° under a load of 400 m of sediment) to be present. This flattening is likely to be caused by the differential rotation of detrital particles under compaction during diagenesis.

Miocene magnetostratigraphy of ODP Site 199-1218 in the equatorial Pacific

Pliocene and Miocene magnetostratigraphy from ODP Site 1218 (Equatorial Pacific) has been obtained by measurements made on u-channel samples, augmented by about 50 discrete samples. U-channel samples were measured at 1 cm intervals and stepwise demagnetized in alternating fields up to a maximum peak field of 80 mT. The component magnetization directions were determined by principal component analysis for demagnetization steps in the 20-60 mT peak field range. A relatively small number of discrete samples were subject to both thermal and alternating field (AF) demagnetization and gave results compatible with u-channel measurements. Magnetostratigraphy from u-channel samples are compared with shipboard data that were based on blanket demagnetization at peak AF fields of 20 mT. U-channel measurements add more detail to the magnetostratigraphic record and allow identification of thin polarity zones especially in the upper part of the section were the sedimentation rates are very low (~2 m/Myr). The component magnetization directions determined from u-channel measurements also gave more reliable and precise estimates of inclination (paleolatitude). The magnetostratigraphy from Site 1218 can be unambiguously correlated with the reference geomagnetic polarity time scale and gives a means of dating the sedimentary sequence. Both Miocene-Pliocene and Oligocene-Miocene stage boundaries were easily identified from the magnetostratigraphic record. Although calculation of paleomagnetic poles is hindered by the low precision of the cores' azimuthal orientation, the data from both u-channel and discrete samples allow determination of the paleolatitude of the Site through time with good precision. Paleomagnetic data indicate that the paleolatitude of Site 1218 has increased form nearly equatorial latitude in the Oligocene to its present-day latitude close to 9°N. Within the precision of the paleomagnetic data, this is in agreement with current predictions of plate motion models based on fixed hotspots.

Orbitally tuned time scale and astronomical forcing in the middle Eocene to early Oligocene determined on ODP and IODP sediment cores

Deciphering the driving mechanisms of Earth system processes, including the climate dynamics expressed as paleoceanographic events, requires a complete, continuous, and high-resolution stratigraphy that is very accurately dated. In this study, we construct a robust astronomically calibrated age model for the middle Eocene to early Oligocene interval (31-43 Ma) in order to permit more detailed study of the exceptional climatic events that occurred during this time, including the Middle Eocene Climate Optimum and the Eocene/Oligocene transition. A goal of this effort is to accurately date the middle Eocene to early Oligocene composite section cored during the Pacific Equatorial Age Transect (PEAT, IODP Exp. 320/321). The stratigraphic framework for the new time scale is based on the identification of the stable long eccentricity cycle in published and new high-resolution records encompassing bulk and benthic stable isotope, calibrated XRF core scanning, and magnetostratigraphic data from ODP Sites 171B-1052, 189-1172, 199-1218, and 207-1260 as well as IODP Sites 320-U1333, and -U1334 spanning magnetic polarity Chrons C12n to C20n. Subsequently we applied orbital tuning of the records to the La2011 orbital solution. The resulting new time scale revises and refines the existing orbitally tuned age model and the Geomagnetic Polarity Time Scale from 31 to 43 Ma. Our newly defined absolute age for the Eocene/Oligocene boundary validates the astronomical tuned age of 33.89 Ma identified at the Massignano (Italy) global stratotype section and point. Our compilation of geochemical records of climate-controlled variability in sedimentation through the middle-to-late Eocene and early Oligocene demonstrates strong power in the eccentricity band that is readily tuned to the latest astronomical solution. Obliquity driven cyclicity is only apparent during very long eccentricity cycle minima around 35.5 Ma, 38.3 Ma and 40.1 Ma.

Hepatic disposition and metabolite kinetics of a homologous series of diflunisal esters

The hepatic disposition and metabolite kinetics of a homologous series of diflunisal O-acyl esters (acetyl, butanoyl, pentanoyl, anti hexanoyl) were determined using a single-pass perfused in situ rat liver preparation. The experiments were conducted using 2% BSA Krebs-Henseleit buffer (pH 7.4), and perfusions were performed at 30 mL/min in each liver. O-Acyl esters of diflunisal and pregenerated diflunisal were injected separately into the portal vein. The venous outflow samples containing the esters and metabolite diflunisal were analyzed by high performance liquid chromatography (HPLC). The normalized outflow concentration-time profiles for each parent ester and the formed metabolite, diflunisal, were analyzed using statistical moments analysis and the two-compartment dispersion model. Data (presented as mean +/- standard error for triplicate experiments) was compared using ANOVA repeated measures, significance level P < 0.05. The hepatic availability (AUC'), the fraction of the injected dose recovered in the outflowing perfusate, for O-acetyldiflunisal (C2D = 0.21 +/- 0.03) was significantly lower than the other esters (0.34-0.38). However, R-N/f(u), the removal efficiency number R-N divided by the unbound fraction in perfusate f(u), which represents the removal efficiency of unbound ester by the liver, was significantly higher for the most lipophilic ester (O-hexanoyldiflunisal, C6D = 16.50 +/- 0.22) compared to the other members of the series (9.57 to 11.17). The most lipophilic ester, C6D, had the largest permeability surface area (PS) product (94.52 +/- 38.20 mt min-l g-l liver) and tissue distribution value VT (35.62 +/- 11.33 mL g(-1) liver) in this series. The MTT of these O-acyl esters of diflunisal were not significantly different from one another. However, the metabolite diflunisal MTTs tended to increase with the increase in the parent ester lipophilicity (11.41 +/- 2.19 s for C2D to 38.63 +/- 9.81 s for C6D). The two-compartment dispersion model equations adequately described the outflow profiles for the parent esters and the metabolite diflunisal formed from the O-acyl esters of diflunisal in the liver.

Integration of MFA and LCA methodologies: the anthropogenic aluminium cycle in Italy

MFA and LCA methodologies were applied to analyse the anthropogenic aluminium cycle in Italy with focus on historical evolution of stocks and flows of the metal, embodied GHG emissions, and potentials from recycling to provide key features to Italy for prioritizing industrial policy toward low-carbon technologies and materials. Historical trend series were collected from 1947 to 2009 and balanced with data from production, manufacturing and waste management of aluminium-containing products, using a ‘top-down’ approach to quantify the contemporary in-use stock of the metal, and helping to identify ‘applications where aluminium is not yet being recycled to its full potential and to identify present and future recycling flows’. The MFA results were used as a basis for the LCA aimed at evaluating the carbon footprint evolution, from primary and electrical energy, the smelting process and the transportation, embodied in the Italian aluminium. A discussion about how the main factors, according to the Kaya Identity equation, they did influence the Italian GHG emissions pattern over time, and which are the levers to mitigate it, it has been also reported. The contemporary anthropogenic reservoirs of aluminium was estimated at about 320 kg per capita, mainly embedded within the transportation and building and construction sectors. Cumulative in-use stock represents approximately 11 years of supply at current usage rates (about 20 Mt versus 1.7 Mt/year), and it would imply a potential of about 160 Mt of CO2eq emissions savings. A discussion of criticality related to aluminium waste recovery from the transportation and the containers and packaging sectors was also included in the study, providing an example for how MFA and LCA may support decision-making at sectorial or regional level. The research constitutes the first attempt of an integrated approach between MFA and LCA applied to the aluminium cycle in Italy.