Analysis of biogenic magnetite nanoparticles

Cobalt doped magnetite (CoxFe3-xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by SQUID, x-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to <4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites.

Paleomagnetic analysis of ODP Site 133-820

Paleomagnetic analysis of sediment samples from Ocean Drilling Program (ODP) Leg 133, Site 820, 10 km from the outer edge of the Great Barrier Reef, is undertaken to investigate the mineral magnetic response to environmental (sea level) changes. Viscous remanent magnetization (VRM) of both multidomain and near-superparamagnetic origin is prevalent and largely obscures the primary remanence, except in isolated high-magnetization zones. The Brunhes/Matuyama boundary cannot be identified, but is expected to be below 120 mbsf. The only evidence that exists for a geomagnetic excursion occurs at about 33 mbsf (-135 k.y.). Only one-half the cores were oriented, and many suffered from internal rotation about the core axis, caused by coring and/or slicing. The decay of magnetic remanence below the surface layer (0-2 mbsf) is attributed to sulfate reduction processes. The magnetic susceptibility (K) record is central for describing and understanding the magnetic properties of the sediments, and their relationship to glacio-eustatic fluctuations in sea level. Three prominent magnetic susceptibility peaks, at about 7, 32, and 64 mbsf, are superimposed on a background of smaller susceptibility oscillations. Fluctuations in susceptibility and remanence in the ôbackgroundö zone are controlled predominantly by variations in the concentration, rather than the composition of ferrimagnetics, with carbonate dilution playing an important role (type-A properties). The sharp susceptibility maxima occur at the start of the marine transgressions following low stands in sea level (high d18O, glacial maxima), and are characterized by a stable single-domain remanence, with a significant contribution from ultra-fine, superparamagnetic grains (type-C properties). During the later marine transgression, the susceptibility gradually returns to low values and the remanence is carried by stable single-domain magnetite (type-B properties). The A, B, and C types of sediment have distinctive ARM/K ratios. Throughout most of the sequence a strong inverse correlation exists between magnetic susceptibility and both CaCO3 and d18O variations. However, in the sharp susceptibility peaks (early transgression), more complex phase relationships are apparent among these parameters. In particular, the K-d18O correlation switches to positive, then reverts to negative during the course of the late transgression, indicating that two distinct mechanisms are responsible for the K-d18O correlation. Lower in the sequence, where sea-level-controlled cycles of upward-coarsening sediments, we find that the initial, mud phase of each cycle has been enriched in high-coercivity magnetic material, which is indicative of more oxic conditions. The main magnetic characteristics of the sediments are thought to reflect sea-level-controlled variations in the sediment source regions and related run-off conditions. Some preliminary evidence is seen that biogenic magnetite may play a significant role in the magnetization of these sediments.

Sedimentological, physical, bulk geochemical, elemental and rock magnetic properties of the Middle to Late Pleistocene Rodderberg (Eifel/Germany)

The sediment record from Rodderberg potentially provides a climate and environmental record spanning at least the last ca 130 ka. Results from a low resolution pilot study reveal characteristic fluctuations that can be related to global climate variability as reflected in marine isotope stages and document the potential of this site for continuous and high-resolution investigations of the Middle to Late Pleistocene. Here we document the tentative lithology drilled, and show how the elemental composition can be interpreted with regard to lake level fluctuations, related redox conditions, but also to grain-size distribution and changes in lacustrine productivity. Finally, based on major lithological changes, a preliminary depth/age model is suggested that allows reassessing published luminescence ages from the same site.

Magnetic susceptibility of deep-sea cores from the Scotia Sea

We studied two deep-sea cores from the Scotia Sea to reconstruct past atmospheric circulation in the southern hemisphere and to resolve a long-standing debate on the interpretation of magnetic susceptibility (MS) records in Southern Ocean (SO) sediment. High-sedimentation sites MD07-3134 (0.2 - 1.2 m/kyr) and MD07-3133 (0.3 - 2 m/kyr) cover the last 92.5 kyr and 36 kyr, respectively. Both exhibit a one-to-one coupling of the MS and Ca2+ signal to the non-sea salt (nss) Ca2+ signal of the EDML ice core, clearly identifying atmospheric circulation as means of distribution. Comparison of additional proxies also excludes major influence by volcanic sources, sea-ice, icebergs, or oceanic current transport. The close resemblance of the dust proxies over the last glacial cycle, in turn, allows for the establishment of an age model of unprecedented resolution and precision for SO deep-sea sediment because atmospheric transport involves no major leads or lags. This is of particular importance because MS is routinely measured on deep-sea cores in the SO but the sediments usually lack biogenic carbonate and therefore had only limited stratigraphic control so far. Southern South America (SSA) is the likely source of eolian material because Site MD07-3133, located closer to the continent, has slightly higher MS values than Site MD07-3134, and also the MS record of Patagonian Site SALSA shows comparable variability. Patagonia was the dust source for both the Scotia Sea and East Antarctica. Dust fluxes were several times higher during glacial times, when atmospheric circulation was either stronger or shifted in latitude, sea level was lowered, shelf surfaces were exposed, and environmental conditions in SSA were dominated by glaciers and extended outwash plains. Hence, MS records of SO deep-sea sediment are reliable tracers of atmospheric circulation, allowing for chronologically-constrained reconstructions of the circum Antarctic paleoclimate history.

Composition of suspended matter and bottom sediments from the Atlantic Ocean and its seas

The book summarizes data on distribution and composition of sedimentary material suspended in waters of the Atlantic Ocean and its seas. Results of observations of Soviet and foreign expeditions are given. Distribution of suspended matter in sections across the ocean, as well as in the most studied seas are shown. New data on grain size, mineral and chemical composition of suspended matter are published. Summary of history of investigation of bottom sediments from the Atlantic Ocean from the first scientific cruises to the present is done. A brief description of sediment types in the ocean and a detailed description of Mediterranean Sea sediments are given.

(Table 1) Magnetic properties of specimens from DSDP Hole 68-503A

Measurements were made of the magnetic properties of 13 sediment samples from cores spanning the entire depth of Hole 503A. The principal aim was to make a preliminary assessment of the magnetic fabric of material obtained from hydraulic piston coring (HPC) which, though considerably bioturbated, might retain substantial traces of any depositional alignment of magnetic grains. Earlier measurements on Deep Sea Drilling Project cores (Rees, 1971; Rees and Frederick, 1974; Hailwood and Sayre, 1979) suggested that the improved HPC sampling technique should, other things being equal, provide good magnetic fabric information. The Hole 503A sediments were known from shipboard measurements to possess comparatively strong stable remanence and therefore seemed likely subjects for this assessment.

Geochemical and rock magnetic investigation of sediment cores of the western South Atlantic

Geochemical and rock magnetic investigations of sediments from three sites on the continental margin off Argentina and Uruguay were carried out to study diagenetic alteration of iron minerals driven by anaerobic oxidation of methane (AOM). The western Argentine Basin represents a suitable sedimentary environment to study nonsteady-state processes because it is characterized by highly dynamic depositional conditions. Mineralogic and bulk solid phase data document that the sediment mainly consists of terrigenous material with high contents of iron minerals. As a typical feature of these deposits, distinct minima in magnetic susceptibility (k) are observed. Pore water data reveal that these minima in susceptibility coincide with the current depth of the sulfate/methane transition (SMT) where HS- is generated by the process of AOM. The released HS- reacts with the abundant iron (oxyhydr)oxides resulting in the precipitation of iron sulfides accompanied by a nearly complete loss of magnetic susceptibility. Modeling of geochemical data suggest that the magnetic record in this area is highly influenced by a drastic change in mean sedimentation rate (SR) which occurred during the Pleistocene/Holocene transition. We assume that the strong decrease in mean SR encountered during this glacial/interglacial transition induced a fixation of the SMT at a specific depth. The stagnation has obviously enhanced diagenetic dissolution of iron (oxyhydr)oxides within a distinct sediment interval. This assumption was further substantiated by numerical modeling in which the mean SR was decreased from 100 cm/kyr during glacial times to 5 cm/kyr in the Holocene and the methane flux from below was fixed to a constant value. To obtain the observed geochemical and magnetic patterns, the SMT must remain at a fixed position for ~9000 yrs. This calculated value closely correlates to the timing of the Pleistocene/Holocene transition. The results of the model show additionally that a constant high mean SR would cause a concave-up profile of pore water sulfate under steady state conditions.

Magnetic and gravity measurements on North-South profiles across the Grosse Meteor Bank, North Atlantic

During the first section of the "Meteor" cruise No. 2 a profile was run from the Azores to the south across the flanks of the Mid-Atlantic Ridge with a chain of seamounts. The profile extended between the Cruiser (living) and the Hyeres seamounts, which, according to our soundings, form a connected massif, and across the centre of the Grosse Meteor Bank (30°N, 28.5 °W). These seamounts rise from a depth of more than 4000 m up till close to the surface of the sea forming there a large almost flat plateau. In the case of the Grosse Meteor Bank, this plateau has a N-S extension of approx. 30 nautical miles and an E-W extension of approx. 20 nautical miles and reaches a height of 275 m in water depth. The gravity measurements yielded a density of the topographic masses of 2.6 g/cm**3 for the Grosse Meteor Bank. Magnitude and shape of the measured free-air anomaly are very well shown in a model computation with this density. The theoretical gravity effects of the seismically detected swell of cristalline rock and of the Moho depression (mountain root) are not indicated by the observational data. It can, therefore, be assumed that the latter two neutralize each other. It seems, accordingly, that there is no local isostatic compensation of the topographic masses. Hence, the density of 2.6 g/cm**3 obtained would be about the true density of rock. In connection with the mean velocity of P waves (Aric et al., 1968) obtained by seismic refraction methods it must be concluded that the material of the 1200-4000 m thick surface layer of the Grosse Meteor Bank consists of consolidated sediments. This finding is supported by the total intensity of the Earth's magnetic field over the Grosse Meteor Bank. On the assumption of a homogeneous magnetization in the direction of the present Earth's field, the computed anomaly of the massif deviates considerably from the measured anomaly while the magnetic field of the seismically detected crystalline body is capable of interpreting the observed data. Deviating from the prevailing interpretation of the seamounts' plateau as a volcanic cone with submarine abrasion, the Grosse Meteor Bank and the seamounts in the vicinity are assumed to be of continental origin. The questions whether these seamounts submerged later on or whether the sealevel has risen subsequently are, therefore, largely nonexistent.

Pliocene to Pleistocene calcium carbonate and organic carbon record of ODP Hole 117-722B

Site 722 provides high resolution records of percent CaCO3, magnetic susceptibility, d18O, organic carbon, and coarse fraction for the past 3.4 m.y. from the crest of the Owen Ridge, northwestern Arabian Sea. Within this time interval, most of the carbonate percent variations can be attributed to terrigenous dilution and do not reflect changes in the carbonate system. From the late Pliocene to Present, the average rate of calcium carbonate accumulation increases from 1 to 3 g/cm**2/k.y. and the average accumulation of organic carbon decreases from 75 to 30 mg/cm**2/k.y. The carbonate component is more dissolved in the older interval. The long-term variations in carbonate accumulation may reflect a greater input of organic matter in the late Pliocene, which decomposes to produce CO2 and dissolve carbonate. Magnetic susceptibility and % noncarbonate (100 - CaCO3%) reflect changes in the amount of the lithogenic component in the sediments. The period of variation of lithogenic material is the same period as the original forcing of the regional summer monsoon, however, the timing matches global aridity patterns and global ice volume (sea level) changes. This preliminary analysis suggests that the high frequency variation of lithogenic material persists for at least the last 3.4 m.y. Within the last million years, calcium carbonate accumulation has a large amplitude signal that covaries with major changes in ice volume. Both calcium carbonate and noncarbonate (mostly terrigenous) accumulation are greatest during glacial stages. Interglacial intervals are characterized by low mass accumulation rates, increased foraminifer fragmentation, and increased opal concentration. The accumulation of organic carbon matches the high frequency changes in sedimentation rates. We attribute this high correlation to enhanced preservation of organic carbon by increased sedimentation rate. Of the three major biological components studied, only opal exhibits the variations expected for a biological productivity system forced by monsoonal upwelling driven by changes in northern hemisphere summer radiation.

Petrography, chemistry and magnetic properties of ODP Leg 115 basalts

A detailed study of the Fe-Ti oxides in four basalt samples-one from each of the four holes drilled into basement on Ocean Drilling Program Leg 115 (Sites 706, 707, 713, and 715) has been performed. Ilmenite is present only in samples from Sites 706 and 715. In the sample from Site 715, Ti-magnetite intergrowths are characteristic of subaerial (?) high-temperature oxy-exsolution; Ti-magnetite in the other three samples has experienced pervasive low-temperature oxidation to Ti-maghemite, as evidenced by the double-humped, irreversible, saturation magnetization vs. temperature (Js/T) curves. The bulk susceptibility of these samples, which are similar in terms of major element chemistry, varies by a factor of ~20 and correlates semiquantitatively with the modal abundance of Fe-Ti spinel, as determined by image analysis with an electron microprobe. The variation in Fe-Ti oxide abundance correlates with average grain size: fine-grained samples contain less Fe-Ti oxide. This prompts the speculation that the crystallization rate may also influence Fe-Ti oxide abundance.

Rock magnetic records and geochemical methods of sediment cores off NW Africa

Two gravity cores retrieved off NW Africa at the border of arid and subtropical environments (GeoB 13602-1 and GeoB 13601-4) were analyzed to extract records of Late Quaternary climate change and sediment export. We apply End Member (EM) unmixing to 350 acquisition curves of isothermal remanent magnetization (IRM). Our approach enables to discriminate rock magnetic signatures of aeolian and fluvial material, to determine biomineralization and reductive diagenesis. Based on the occurrence of pedogenically formed magnetic minerals in the fluvial and aeolian EMs, we can infer that goethite formed in favor to hematite in more humid climate zones. The diagenetic EM dominates in the lower parts of the cores and within a thin near-surface layer probably representing the modern Fe**2+/Fe**3+ redox boundary. Up to 60% of the IRM signal is allocated to a biogenic EM underlining the importance of bacterial magnetite even in siliciclastic sediments. Magnetosomes are found well preserved over most of the record, indicating suboxic conditions. Temporal variations of the aeolian and fluvial EMs appear to faithfully reproduce and support trends of dry and humid conditions on the continent. The proportion of aeolian to fluvial material was dramatically higher during Heinrich Stadials, especially during Heinrich Stadial 1. Dust export from the Arabian-Asian corridor appears to vary contemporaneous to increased dust fluxes on the continental margin of NW Africa emphasizing that melt-water discharge in the North Atlantic had an enormous impact on atmospheric dynamics.

Sedimentologic and magnetic data of sediment cores on the western slope of the Mid-Atlantic Ridge

The relative paleointensity (RPI) method assumes that the intensity of post depositional remanent magnetization (PDRM) depends exclusively on the magnetic field strength and the concentration of the magnetic carriers. Sedimentary remanence is regarded as an equilibrium state between aligning geomagnetic and randomizing interparticle forces. Just how strong these mechanical and electrostatic forces are, depends on many petrophysical factors related to mineralogy, particle size and shape of the matrix constituents. We therefore test the hypothesis that variations in sediment lithology modulate RPI records. For 90 selected Late Quaternary sediment samples from the subtropical and subantarctic South Atlantic Ocean a combined paleomagnetic and sedimentological dataset was established. Misleading alterations of the magnetic mineral fraction were detected by a routine Fe/kappa test (Funk, J., von Dobeneck, T., Reitz, A., 2004. Integrated rock magnetic and geochemical quantification of redoxomorphic iron mineral diagenesis in Late Quaternary sediments from the Equatorial Atlantic. In: Wefer, G., Mulitza, S., Ratmeyer, V. (Eds.), The South Atlantic in the Late Quaternary: reconstruction of material budgets and current systems. Springer-Verlag, Berlin/Heidelberg/New York/Tokyo, pp. 239-262). Samples with any indication of suboxic magnetite dissolution were excluded from the dataset. The parameters under study include carbonate, opal and terrigenous content, grain size distribution and clay mineral composition. Their bi- and multivariate correlations with the RPI signal were statistically investigated using standard techniques and criteria. While several of the parameters did not yield significant results, clay grain size and chlorite correlate weakly and opal, illite and kaolinite correlate moderately to the NRM/ARM signal used here as a RPI measure. The most influential single sedimentological factor is the kaolinite/illite ratio with a Pearson's coefficient of 0.51 and 99.9% significance. A three-member regression model suggests that matrix effects can make up over 50% of the observed RPI dynamics.