Influence of nanoparticle size on the nonlinear optical properties of magnetite ferrofluids

The nonlinear index of refraction (n(2)) and the two-photon absorption coefficient (beta) of water-based ferrofluids made of magnetite nanocrystals of different sizes and with different coatings have been measured through the Z-scan technique, with ultrashort (femtoseconds) laser pulses. Their third-order susceptibility is calculated from the values of n(2) and beta. The influence of different particles' coatings and sizes on these nonlinear optical properties are investigated. The values of n(2) and beta depend more significantly on the nanoparticles' size than on the particular coating. We observe a decrease of beta as the nanoparticles' diameters decrease, although the optical gap is found to be the same for all samples. The results are interpreted considering modifications in the electronic orbital shape due to the particles' nanosize effect.

Magnetic Properties of γ - Fe2O3 Nanoparticles at the Verge of Nucleation Process.

A low-energy new method based in a one-step synthesis at room temperature produces very small maghemite nanopar ticles. The fast neutralization reaction (co-precipitation) of a ferric solution (FeCl3 aqueous) in a basic medium (NH4OH concentrated) produces an intermediate phase, presumably two-line ferrihydrite, that in oxidizing conditions is transformed to maghemite nanopar ticles. That “primordial soup” is characterized by small atom arrangements that are the base for maghemite tiny crystals. The final product of the reaction was characterized by X-ray diffraction, high-resolution transmission electron microscopy, X-ray absorption fine structure, Mössbauer spectroscopy, and magnetometry.

Sintesi di nanoparticelle polimeriche basate su acido(D,L-lattico-co-glicolico) per applicazioni in nanomedicina

Questo lavoro di tesi rientra nel progetto europeo SaveMe, al quale partecipa il gruppo di ricerca del dipartimento di chimica organica nel quale ho svolto l’attività di tirocinio. Obiettivo finale di tale progetto è la sintesi di nanoparticelle a base di PLGA (acido poli(D,L-lattico-co-glicolico)) superficialmente funzionalizzate con biomolecole, per l’impiego nel trattamento e nella diagnosi del cancro al pancreas. L’obiettivo da raggiungere nel primo anno di ricerca per il mio gruppo era la sintesi delle nanoparticelle centrali (core nanosystems). Nel presente lavoro sono quindi riportati i metodi di sintesi di polimeri derivati da PLGA e suoi copolimeri con PEG (polietilenglicole) aventi vari gruppi funzionali terminali: acidi idrossamici, amminici e acidi carbossilici. I polimeri sintetizzati sono stati caratterizzati tramite test colorimetrici qualitativi, 1H-NMR, 13C-NMR, spettrometria IR e TGA. Sono state sintetizzate nanoparticelle polimeriche (PNPs), con le tecniche Oil/Water (O/W) e nanoprecipitazione (NP), basate sui polimeri ottenuti, aventi quindi funzioni acide, idrossamiche ed amminiche sulla superficie. Su queste PNPs è stato effettuata una decorazione superficiale con nanoparticelle metalliche di maghemite (CAN-Maghemite). Le nanoparticelle polimeriche sono state caratterizzate tramite DLS e delle PNPs decorate sono state ottenute immagini TEM. Sono riportati inoltre i test di viabilità cellulare delle nanoparticelle ottenute.

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Holocene sediment transport from the glaciated margin of East/Northeast Greenland to the N Iceland shelves

We examine variations in the ice-rafted sources for sediments in the Iceland/East Greenland offshore marine archives by utilizing a sediment unmixing model and link the results to a coupled iceberg-ocean model. Surface samples from around Iceland and along the E/NE Greenland shelf are used to define potential sediment sources, and these are examined within the context of the down-core variations in mineralogy in the <2 mm sediment fraction from a transect of cores across Denmark Strait. A sediment unmixing model is used to estimate the fraction of sediment <2 mm off NW and N Iceland exported across Denmark Strait; this averaged between 10 and 20%. Both the sediment unmixing model and the coupled iceberg-ocean model are consistent in finding that the fraction of "far-travelled" sediments in the Denmark Strait environs is overwhelmingly of local, mid-East Greenland, provenance, and therefore with a significant cross-channel component to their travel. The Holocene record of ice-rafted sediments denotes a three-part division of the Holocene in terms of iceberg sediment transport with a notable increase in the process starting ca 4000 cal yr BP. This latter increase may represent the re-advance during the Neoglacial period of land-terminating glaciers on the Geikie Plateau to become marine-terminating. The contrast in spectral signals between these cores and the 1500-yr cycle at VM28-14, just south of the Denmark Strait, combined with the coupled iceberg-model results, leads us to speculate that the signal at VM28-14 reflects pulses in overflow waters, rather than an ice-rafted signal.

(Table 1) Mineralogical composition of sediments from DSDP Sites 69-504 and 69-505

We discuss the provenance of minerals detected by X-ray-diffraction analyses of sediments of Sites 504 and 505 of Deep Sea Drilling Project Leg 69. These are X-ray-amorphous material, opal-CT, calcite, quartz, feldspar, apatite, smectite, illite, kaolinite, magnetite, maghemite, pyrite, marcasite, barite, sepiolite, and clinoptilolite. Authigenic marcasite and clinoptilolite together with opal-CT are restricted to Site 504, indicating the special diagenetic conditions related to relatively high sediment temperatures at this site. Marcasite formation is likely dependent on the relatively low pH values of <7.1 found in interstitial waters of Site 504 sediments below 50 meters sub-bottom. Clinoptilolite evidently was formed by diagenetic alteration of rhyolitic volcanic glass or smectite plus biogenic silica within the chalk-limestone-chert sequence of Site 504, where opal-CT also reflects a high degree of silica dissolution and reprecipitation. This was a consequence of high temperatures (50-55 °C) at the base of the sediment column.

Rock magnetic properties of ODP Hole 109-670A

The magnetic properties of 11 samples from Site 670 of Leg 109, 3 harzburgites and 8 highly serpentinized peridotites, have been studied. Reflected light microscopy and Curie temperatures confirm that magnetite is the dominant magnetic mineral in all samples. However, both rock types show different magnetic behavior. Susceptibility, saturation magnetization, and NRM are higher for the serpentinites, because of the higher magnetite content. The hysteresis parameters indicate magnetite particles with pseudosingle domain structure for both rock types. For the remarkable anisotropy of the magnetic susceptibility no definite explanation could be found, because of the complex texture of the samples. In both rock types the presence of maghemite, a product of low temperature oxidation of magnetite, has been indicated by reflected light microscopy and by thermomagnetic analysis. As the maghemite converts to hematite at temperatures above 350°C, the temperature during the serpentinization was below this value assuming that the maghemitization took place at the same time.

Sediment composition in NE Greenland Fjords, Shelf, and Slope

In order to document changes in Holocene glacier extent and activity in NE Greenland (~73° N) we study marine sediment records that extend from the fjords (PS2631 and PS2640), across the shelf (PS2623 and PS2641), to the Greenland Sea (JM07-174GC). The primary bedrock geology of the source areas is the Caledonian sediment outcrop, including Devonian red beds, plus early Neoproterozoic gneisses and early Tertiary volcanics. We examine the variations in colour (CIE*), grain size, and bulk mineralogy (from X-ray diffraction of the <2 mm sediment fraction). Fjord core PS2640 in Sofia Sund, with a marked red hue, is distinct in grain size, colour and mineralogy from the other fjord and shelf cores. Five distinct grain-size modes are distinguished of which only one is associated with a coarse ice-rafting signal - this mode is rare in the mid- and late Holocene. A sediment unmixing program (SedUnMixMC) is used to characterize down-core changes in sediment composition based on the upper late Holocene sediments from cores PS2640 (Sofia Sund), PS2631 (Kaiser Franz Joseph Fjord) and PS2623 (south of Shannon Is), and surface samples from the Kara Sea (as an indicator of transport from the Russian Arctic shelves). Major changes in mineral composition are noted in all cores with possible coeval shifts centred c. 2.5, 4.5 and 7.5 cal. ka BP (±0.5 ka) but are rarely linked with changes in the grain-size spectra. Coarse IRD (>2 mm) and IRD-grain-size spectra are rare in the last 9-10 cal. ka BP and, in contrast with areas farther south (~68° N), there is no distinct IRD signal at the onset of neoglaciation. Our paper demonstrates the importance of the quantitative analysis of sediment properties in clarifying source to sink changes in glacial marine environments.

Paleomagnetic of ODP Leg 133 holes

Paleomagnetic and rock-magnetic analyses from discrete samples of carbonate sites on the Queensland Plateau were used to determine magnetic polarity reversal stratigraphy and the nature of magnetization in these sediments. Magnetic polarity zones were correlated with the geomagnetic polarity time scale in the upper portions of cores at Sites 812 through 814, usually back to a late Pliocene age. Loss of reliable directional data was coincidental with a major decrease in magnetic intensity, below which, no stable polarity zones could be identified. The intensity reduction is either an in-situ alteration of magnetic grains, or an input signal representing progressive increase in the magnetic component of Queensland Plateau sediments. Although not conclusive at this point, the geochemical conditions and differing age of intensity reduction support the former hypothesis. Rock-magnetic analysis of carbonate sediments suggests that ultrafine-grained magnetite or maghemite crystals is an important carrier of remanence and may be biogenic in origin. Application of a recently calibrated anhysteretic remanent magnetization test to assess configuration of single-domain crystal within a natural matrix indicates that cementation (ooze-chalk-limestone) may be important in post-depositional changes affecting magnetostatic grain interaction.

XRD mineralogy of sediments from the Greenland east coast

Quantitative X-Ray Diffraction (qXRD) analysis of the <2 mm sediment fraction from surface (sea floor) samples, and marine sediment cores that span the last 10-12 cal ka BP, are used to describe spatial and temporal variations in non-clay mineral compositions for an area between Kangerlussuaq Trough and Scoresby Sund (?67°-70°N), East Greenland. Bedrock consists primarily of an early Tertiary alkaline complex with high weight% of pyroxene and plagioclase. Farther inland and to the north, the bedrock is dominantly felsic with a high fraction of quartz and potassium feldspars. Principal Component (PC) analysis of the non-clay sediment compositions indicates the importance of quartz and pyroxene as compositional end members, with an abrupt shift from quartz and k-feldspar dominated sediments north of Scoresby Sund to sediments rich in pyroxene and plagioclase feldspars offshore from the early Tertiary basaltic outcrop. Coarse (<2 mm or <1 mm) ice-rafted sediments are largely absent from the trough sediments between ?8 and 5 cal ka BP, but then increase in the last 4 cal ka BP. Compositional unmixing of the sediments in Grivel Basin and Kangerlussuaq Trough indicate the dominance of local over long distance sediment sources, with pulses of sediment from tidewater glaciers in Kangerlussuaq and Nansen fjords reaching the inner shelf during the Neoglaciation. The change in IRD is more dramatic in the sediment grain-size proxies than in the quartz wt%. Forty to seventy percent of the variance in the quartz records from either side of Denmark Strait is explained by low frequency trends, but the data from the Grivel Basin, East Greenland, are distinctly different, with an approximate 2500 yr periodicity.