Chemistry and grain-size distribution of terrigenous sediments deposited at Site GeoB9501

The Sahara Desert is the largest source of mineral dust in the world. Emissions of African dust increased sharply in the early 1970s, a change that has been attributed mainly to drought in the Sahara/Sahel region caused by changes in the global distribution of sea surface temperature. The human contribution to land degradation and dust mobilization in this region remains poorly understood, owing to the paucity of data that would allow the identification of long-term trends in desertification. Direct measurements of airborne African dust concentrations only became available in the mid-1960s from a station on Barbados and subsequently from satellite imagery since the late 1970s: they do not cover the onset of commercial agriculture in the Sahel region ~170 years ago. Here we construct a 3,200-year record of dust deposition off northwest Africa by investigating the chemistry and grain-size distribution of terrigenous sediments deposited at a marine site located directly under the West African dust plume. With the help of our dust record and a proxy record for West African precipitation we find that, on the century scale, dust deposition is related to precipitation in tropical West Africa until the seventeenth century. At the beginning of the nineteenth century, a sharp increase in dust deposition parallels the advent of commercial agriculture in the Sahel region. Our findings suggest that human-induced dust emissions from the Sahel region have contributed to the atmospheric dust load for about 200 years.

He isotope, U/Th isotope, Calcium carbonate, biogenic opal, rare earth element concentrations, and grain size distribution measured on core-top sediments during SONNE cruise SO202 (INOPEX)

Eolian dust is a significant source of iron and other nutrients that are essential for the health of marine ecosystems and potentially a controlling factor of the high nutrient-low chlorophyll status of the Subarctic North Pacific. We map the spatial distribution of dust input using three different geochemical tracers of eolian dust, 4He, 232Th and rare earth elements, in combination with grain size distribution data, from a set of core-top sediments covering the entire Subarctic North Pacific. Using the suite of geochemical proxies to fingerprint different lithogenic components, we deconvolve eolian dust input from other lithogenic inputs such as volcanic ash, ice-rafted debris, riverine and hemipelagic input. While the open ocean sites far away from the volcanic arcs are dominantly composed of pure eolian dust, lithogenic components other than eolian dust play a more crucial role along the arcs. In sites dominated by dust, eolian dust input appears to be characterized by a nearly uniform grain size mode at ~4 µm. Applying the 230Th-normalization technique, our proxies yield a consistent pattern of uniform dust fluxes of 1-2 g/m**2/yr across the Subarctic North Pacific. Elevated eolian dust fluxes of 2-4 g/m**2/yr characterize the westernmost region off Japan and the southern Kurile Islands south of 45° N and west of 165° E along the main pathway of the westerly winds. The core-top based dust flux reconstruction is consistent with recent estimates based on dissolved thorium isotope concentrations in seawater from the Subarctic North Pacific. The dust flux pattern compares well with state-of-the-art dust model predictions in the western and central Subarctic North Pacific, but we find that dust fluxes are higher than modeled fluxes by 0.5-1 g/m**2/yr in the northwest, northeast and eastern Subarctic North Pacific. Our results provide an important benchmark for biogeochemical models and a robust approach for downcore studies testing dust-induced iron fertilization of past changes in biological productivity in the Subarctic North Pacific.

San Francisco Coastal System grain size and geochemical data for sand provenance study

Over 150 million cubic meter of sand-sized sediment has disappeared from the central region of the San Francisco Bay Coastal System during the last half century. This enormous loss may reflect numerous anthropogenic influences, such as watershed damming, bay-fill development, aggregate mining, and dredging. The reduction in Bay sediment also appears to be linked to a reduction in sediment supply and recent widespread erosion of adjacent beaches, wetlands, and submarine environments. A unique, multi-faceted provenance study was performed to definitively establish the primary sources, sinks, and transport pathways of beach sized-sand in the region, thereby identifying the activities and processes that directly limit supply to the outer coast. This integrative program is based on comprehensive surficial sediment sampling of the San Francisco Bay Coastal System, including the seabed, Bay floor, area beaches, adjacent rock units, and major drainages. Analyses of sample morphometrics and biological composition (e.g., Foraminifera) were then integrated with a suite of tracers including 87Sr/86Sr and 143Nd/144Nd isotopes, rare earth elements, semi-quantitative X-ray diffraction mineralogy, and heavy minerals, and with process-based numerical modeling, in situ current measurements, and bedform asymmetry to robustly determine the provenance of beach-sized sand in the region.

Size-partitioned phytoplankton carbon concentrations retrieved from ocean color data, links to data in netCDF format

Owing to their important roles in biogeochemical cycles, phytoplankton functional types (PFTs) have been the aim of an increasing number of ocean color algorithms. Yet, none of the existing methods are based on phytoplankton carbon (C) biomass, which is a fundamental biogeochemical and ecological variable and the "unit of accounting" in Earth system models. We present a novel bio-optical algorithm to retrieve size-partitioned phytoplankton carbon from ocean color satellite data. The algorithm is based on existing methods to estimate particle volume from a power-law particle size distribution (PSD). Volume is converted to carbon concentrations using a compilation of allometric relationships. We quantify absolute and fractional biomass in three PFTs based on size - picophytoplankton (0.5-2 µm in diameter), nanophytoplankton (2-20 µm) and microphytoplankton (20-50 µm). The mean spatial distributions of total phytoplankton C biomass and individual PFTs, derived from global SeaWiFS monthly ocean color data, are consistent with current understanding of oceanic ecosystems, i.e., oligotrophic regions are characterized by low biomass and dominance of picoplankton, whereas eutrophic regions have high biomass to which nanoplankton and microplankton contribute relatively larger fractions. Global climatological, spatially integrated phytoplankton carbon biomass standing stock estimates using our PSD-based approach yield - 0.25 Gt of C, consistent with analogous estimates from two other ocean color algorithms and several state-of-the-art Earth system models. Satisfactory in situ closure observed between PSD and POC measurements lends support to the theoretical basis of the PSD-based algorithm. Uncertainty budget analyses indicate that absolute carbon concentration uncertainties are driven by the PSD parameter No which determines particle number concentration to first order, while uncertainties in PFTs' fractional contributions to total C biomass are mostly due to the allometric coefficients. The C algorithm presented here, which is not empirically constrained a priori, partitions biomass in size classes and introduces improvement over the assumptions of the other approaches. However, the range of phytoplankton C biomass spatial variability globally is larger than estimated by any other models considered here, which suggests an empirical correction to the No parameter is needed, based on PSD validation statistics. These corrected absolute carbon biomass concentrations validate well against in situ POC observations.

Grain size distribution and bulk chemistry of eolian dust

Atmospheric dust samples collected along a transect off the West African coast have been investigated for their physical (grain-size distribution), mineralogical, and chemical (major elements) composition. On the basis of these data the samples were grouped into sets of samples that most likely originated from the same source area. In addition, shipboard-collected atmospheric meteorological data, modeled 4-day back trajectories for each sampling day and location, and Total Ozone Mapping Spectrometer aerosol index data for the time period of dust collection (February-March 1998) were combined and used to reconstruct the sources of the groups of dust samples. On the basis of these data we were able to determine the provenance of the various dust samples. It appears that the bulk of the wind-blown sediments that are deposited in the proximal equatorial Atlantic Ocean are transported in the lower level (>~900 hPa) NE trade wind layer, which is a very dominant feature north of the Intertropical Convergence Zone (ITCZ). However, south of the surface expression of the ITCZ, down to 5°S, where surface winds are southwesterly, we still collected sediments that originated from the north and east, carried there by the NE trade wind layer, as well as by easterly winds from higher altitudes. The fact that the size of the wind-blown dust depends not only on the wind strength of the transporting agent but also on the distance to the source hampers a direct comparison of the dust's size distributions and measured wind strengths. However, a comparison between eolian dust and terrigenous sediments collected in three submarine sediment traps off the west coast of NW Africa shows that knowledge of the composition of eolian dust is a prerequisite for the interpretation of paleorecords obtained from sediment cores in the equatorial Atlantic.

Grain size effects on excess Thorium-230 of sediment cores from the Southern Ocean and the South East Atlantic

Excess Thorium-230 (230Thxs) as a constant flux tracer is an essential tool for paleoceanographic studies, but its limitations for flux normalization are still a matter of debate. In regions of rapid sediment accumulation, it has been an open question if 230Thxs-normalized fluxes are biased by particle sorting effects during sediment redistribution. In order to study the sorting effect of sediment transport on 230Thxs, we analyzed the specific activity of 230Thxs in different particle size classes of carbonate-rich sediments from the South East Atlantic, and of opal-rich sediments from the Atlantic sector of the Southern Ocean. At both sites, we compare the 230Thxs distribution in neighboring high vs. low accumulation settings. Two grain-size fractionation methods are explored. We find that the 230Thxs distribution is strongly grain size dependent, and 50-90% of the total 230Thxs inventory is concentrated in fine material smaller than 10 µm, which is preferentially deposited at the high accumulation sites. This leads to an overestimation of the focusing factor Psi, and consequently to an underestimation of the vertical flux rate at such sites. The distribution of authigenic uranium indicates that fine organic-rich material has also been re-deposited from lateral sources. If the particle sorting effect is considered in the flux calculations, it reduces the estimated extent of sediment focusing. In order to assess the maximum effect of particle sorting on Psi, we present an extreme scenario, in which we assume a lateral sediment supply of only fine material (< 10 µm). In this case, the focusing factor of the opal-rich core would be reduced from Psi = 5.9 to Psi = 3.2. In a more likely scenario, allowing silt-sized material to be transported, Psi is reduced from 5.9 to 5.0 if particle sorting is taken into consideration. The bias introduced by particle sorting is most important for strongly focused sediments. Comparing 230Thxs-normalized mass fluxes biased by sorting effects with uncorrected mass fluxes, we suggest that 230Thxs-normalization is still a valid tool to correct for lateral sediment redistribution. However, differences in focusing factors between core locations have to be evaluated carefully, taking the grain size distributions into consideration.

Grain size distribution and sea level changes in Gåsfjärden fjord

We analysed long-term variations in grain-size distribution in sediments from Gåsfjärden, a fjord-like inlet on the south-west Baltic Sea, and explored potential drivers of the recorded changes in sediment grain-size data. Over the last 5.4 thousand years (ka), the relative sea level decreased 17 m in the study region, caused by isostatic land uplift. As a consequence, Gåsfjärden has been transformed from an open coastal setting into a semi-closed inlet surrounded on the east by numerous small islands. To quantitatively estimate the morphological changes in Gåsfjärden over the last 5.4 ka and to further link the changes to our grain-size data, a digital elevation model (DEM)-based openness index was calculated. In the period between 5.4 and 4.4 ka BP, the inlet was characterised by the largest openness index. During this interval, the highest sand contents (~0.4 %) and silt/clay ratios (~0. 3) in the sediment sequence were recorded, indicating relatively high bottom water energy. After 4.4 ka BP, the average sand content was halved to ~0.2 % and the silt/clay ratios showed a significant decreasing trend over the last 4 ka. These changes are found to be associated with the gradual embayment of Gåsfjärden as represented in the openness index. The silt/clay ratios exhibited a delayed and slower change compared with the sand contents, which further suggest that finer particles are less sensitive to changes in hydrodynamic energy. Our DEM-based coastal openness index has proved to be a useful tool for interpreting the sedimentary grain-size record.

Enviromagnetic, major element, and grain-size analyses of surface sediment samples along the continental margin between East Brazil and Patagonia

Continental margin sediments of SE South America originate from various terrestrial sources, each conveying specific magnetic and element signatures. Here, we aim to identify the sources and transport characteristics of shelf and slope sediments deposited between East Brazil and Patagonia (20°-48°S) using enviromagnetic, major element, and grain-size data. A set of five source-indicative parameters (i.e., chi-fd%, ARM/IRM, S0.3T, SIRM/Fe and Fe/K) of 25 surface samples (16-1805 m water depth) was analyzed by fuzzy c-means clustering and non-linear mapping to depict and unmix sediment-province characteristics. This multivariate approach yields three regionally coherent sediment provinces with petrologically and climatically distinct source regions. The southernmost province is entirely restricted to the slope off the Argentinean Pampas and has been identified as relict Andean-sourced sands with coarse unaltered magnetite. The direct transport to the slope was enabled by Rio Colorado and Rio Negro meltwaters during glacial and deglacial phases of low sea level. The adjacent shelf province consists of coastal loessoidal sands (highest hematite and goethite proportions) delivered from the Argentinean Pampas by wave erosion and westerly winds. The northernmost province includes the Plata mudbelt and Rio Grande Cone. It contains tropically weathered clayey silts from the La Plata Drainage Basin with pronounced proportions of fine magnetite, which were distributed up to ~24° S by the Brazilian Coastal Current and admixed to coarser relict sediments of Pampean loessoidal origin. Grain-size analyses of all samples showed that sediment fractionation during transport and deposition had little impact on magnetic and element source characteristics. This study corroborates the high potential of the chosen approach to access sediment origin in regions with contrasting sediment sources, complex transport dynamics, and large grain-size variability.

Particle characterization at CVAO during the 2007 RHaMBLe intensive

The chemical characterization of filter high volume (HV) and Berner impactor (BI) samples PM during RHaMBLe (Reactive Halogens in the Marine Boundary Layer) 2007 shows that the Cape Verde aerosol particles are mainly composed of sea salt, mineral dust and associated water. Minor components are nss-salts, OC and EC. The influence from the African continent on the aerosol constitution was generally small but air masses which came from south-western Europe crossing the Canary Islands transported dust to the sampling site together with other loadings. The mean mass concentration was determined for PM10 to 17 µg/m**3 from impactor samples and to 24.2 µg/m**3 from HV filter samples. Non sea salt (nss) components of PM were found in the submicron fractions and nitrate in the coarse mode fraction. Bromide was found in all samples with much depleted concentrations in the range 1-8 ng/m**3 compared to fresh sea salt aerosol indicating intense atmospheric halogen chemistry. Loss of bromide by ozone reaction during long sampling time is supposed and resulted totally in 82±12% in coarse mode impactor samples and in filter samples in 88±6% bromide deficits. A chloride deficit was determined to 8% and 1% for the coarse mode particles (3.5-10 µm; 1.2-3.5 µm) and to 21% for filter samples. During 14 May with high mineral dust loads also the maximum of OC (1.71 µg/m**3) and EC (1.25 µg/m**3) was measured. The minimum of TC (0.25 µg/m**3) was detected during the period 25 to 27 May when pure marine air masses arrived. The concentrations of carbonaceous material decrease with increasing particle size from 60% for the ultra fine particles to 2.5% in coarse mode PM. Total iron (dust vs. non-dust: 0.53 vs. 0.06 µg/m**3), calcium (0.22 vs. 0.03 µg/m**3) and potassium (0.33 vs. 0.02 µg/m**3) were found as good indicators for dust periods because of their heavily increased concentration in the 1.2 to 3.5 µm fraction as compared to their concentration during the non-dust periods. For the organic constituents, oxalate (78-151 ng/m**3) and methanesulfonic acid (MSA, 25-100 ng/m**3) are the major compounds identified. A good correlation between nss-sulphate and MSA was found for the majority of days indicating active DMS chemistry and low anthropogenic influences.

Characterisation of polyethylene powders for rotational moulding and effect of powder size and shape on densification behaviour

The particle size, shape and distribution of a range of rotational moulding polyethylenes (PEs) ground to powder was investigated using a novel visual data acquisition and analysis system (TP Picture®), developed by Total Petrochemicals. Differences in the individual particle shape factors of the powder samples were observed and correlations with the grinding conditions were determined. When heated, the bubble dissolution behaviour of the same powders was investigated and the shape factor correlated with densification rate, bubble size and bubble distribution.

Investigation of the Nucleation and Growth of Colloidal Indium Phosphide: from Molecular Precursors to Semiconductor Nanocrystals through In37P20(O2CR)51 as a Magic-Size Intermediate

Thesis (Ph.D.)--University of Washington, 2016-06

Effect of particle loss on soil behaviour.

Soil particle loss can result in strength and volume reductions which are difficult to predict. This paper investigates the influence of the removal of fractions of selected particle sizes under different confining pressures. The mass loss process was reproduced by the dissolution of selected salt particle sizes and fractions from uniform Leighton Buzzard sand. The dissolution tests were performed in a triaxial cell customised to allow circulation of pore-fluid thereby allowing the dissolution/removal of the salt fraction. Test results from previously conducted oedometric dissolution tests and subsequent triaxial dissolution tests all show increases in void ratio. From the triaxial tests, a reduction in shear strength with increasing ductility was observed. Volumetric and strength behaviour were found to be related to the particle size and fraction material removed while shear-wave measurements obtained pre- and post-particle removal indicate significant changes in small-strain stiffness.

CONTROL OF SIZE AND MAGNETIC PROPERTIES OF CARBOXYL-FUNCTIONALIZED MAGNETITE PARTICLES: SYNTHESIS PROCEDURES, CHARACTERIZATIONS, AND APPLICATIONS

Magnetic nanoparticles (MNPs) are known for the unique properties conferred by their small size and have found wide application in food safety analyses. However, their high surface energy and strong magnetization often lead to aggregation, compromising their functions. In this study, iron oxide magnetic particles (MPs) over the range of nano to micro size were synthesized, from which particles with less aggregation and excellent magnetic properties were obtained. MPs were synthesized via three different hydrothermal procedures, using poly (acrylic acid) (PAA) of different molecular weight (Mw) as the stabilizer. The particle size, morphology, and magnetic properties of the MPs from these synthesis procedures were characterized and compared. Among the three syntheses, one-step hydrothermal synthesis demonstrated the highest yield and most efficient magnetic collection of the resulting PAA-coated magnetic microparticles (PAA-MMPs, >100 nm). Iron oxide content of these PAA-MMPs was around 90%, and the saturation magnetization ranged from 70.3 emu/g to 57.0 emu/g, depending on the Mw of PAA used. In this approach, the particles prepared using PAA with Mw of 100K g/mol exhibited super-paramagnetic behavior with ~65% lower coercivity and remanence compared to others. They were therefore less susceptible to aggregation and remained remarkably water-dispersible even after one-month storage. Three applications involving PAA-MMPs from one-step hydrothermal synthesis were explored: food proteins and enzymes immobilization, antibody conjugation for pathogen capture, and magnetic hydrogel film fabrication. These studies demonstrated their versatile functions as well as their potential applications in the food science area.

The Applicability Of Ordered Mesoporous Sba-15 And Its Hydrophobic Glutaraldehyde-bridge Derivative To Improve Ibuprofen-loading In Releasing System.

The mesoporous SBA-15 silica with uniform hexagonal pore, narrow pore size distribution and tuneable pore diameter was organofunctionalized with glutaraldehyde-bridged silylating agent. The precursor and its derivative silicas were ibuprofen-loaded for controlled delivery in simulated biological fluids. The synthesized silicas were characterized by elemental analysis, infrared spectroscopy, (13)C and (29)Si solid state NMR spectroscopy, nitrogen adsorption, X-ray diffractometry, thermogravimetry and scanning electron microscopy. Surface functionalization with amine containing bridged hydrophobic structure resulted in significantly decreased surface area from 802.4 to 63.0 m(2) g(-1) and pore diameter 8.0-6.0 nm, which ultimately increased the drug-loading capacity from 18.0% up to 28.3% and a very slow release rate of ibuprofen over the period of 72.5h. The in vitro drug release demonstrated that SBA-15 presented the fastest release from 25% to 27% and SBA-15GA gave near 10% of drug release in all fluids during 72.5 h. The Korsmeyer-Peppas model better fits the release data with the Fickian diffusion mechanism and zero order kinetics for synthesized mesoporous silicas. Both pore sizes and hydrophobicity influenced the rate of the release process, indicating that the chemically modified silica can be suggested to design formulation of slow and constant release over a defined period, to avoid repeated administration.