Pore structure characterization of kaolin, metakaolin, and their acid-treated products using small-angle X-ray scattering

Pore structure of dealuminated kaolin and metakaolin was studied by small-angle X-ray scattering (SAXS). Both parent kaolin and metakaolin have about 10% of the total pore volume provided by globular pores with 105 Å mean pore size. Their surface area is about 14 m2/g. Acid dealumination of kaolin causes an increase of its globular pore volume without an appreciable change in the mean pore size, its surface area increasing up to about 90 m2/g. Acid dealumination of metakaolin enhances the globular pore volume, although there is generation of slit-shaped pores with a narrow thickness distribution whose mean value is 14 Å. This interlayer spacing causes an increase in surface area of about 190 m2/g by SAXS. © 1994.

Morphological prediction of worker size discrimination and relative abundance of sympartic species of Pseudacteon (Dipt., Phoridae) parasitoids of the fire ant, Solenopsis saevissima (Hym., Formicidae) in Brazil

Patterns of attack for collected species of phorids are predicted using multivariate morphometrics of female Pseudacteon species and worker size distributions of parasitized fire ants, Solenopsis saevissima. The model assumes that there is a direct correlation between phorid size and the size range of the worker ant attacked, and presumes that worker sizes are a resource that is divided by sympatric phorid species to minimize joint parasitism. These results suggest that the community of sympatric Pseudacteon species on only one host species coexists by restricting the size of workers attacked, and secondarily by differing diel patterns of ovipositional activity. When we compared relative abundance of species of Pseudacteon with the size distribution of foragers of S. saevissima, our observed distribution did not differ significantly from our predicted relative abundance of females of Pseudacteon. The activity of Pseudacteon may be a factor determining forager size distributions.

About the thermal stability and pore elimination in the ordered hexagonal mesoporous silica SBA-15

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Invariant Solutions of Richards' Equation for Water Movement in Dissimilar Soils

Scaling methods allow a single solution to Richards' equation (RE) to suffice for numerous specific cases of water flow in unsaturated soils. During the past half-century, many such methods were developed for similar soils. In this paper, a new method is proposed for scaling RE for a wide range of dissimilar soils. Exponential-power (EP) functions are used to reduce the dependence of the scaled RE on the soil hydraulic properties. To evaluate the proposed method, the scaled RE was solved numerically considering two test cases: infiltration into relatively dry soils having initially uniform water content distributions, and gravity-dominant drainage occurring from initially wet soil profiles. Although the results for four texturally different soils ranging from sand to heavy clay (adopted from the UNSODA database) showed that the scaled solution were invariant for a wide range of flow conditions, slight deviations were observed when the soil profile was initially wet in the infiltration case or deeply wet in the drainage case. The invariance of the scaled RE makes it possible to generalize a single solution of RE to many dissimilar soils and conditions. Such a procedure reduces the numerical calculations and provides additional opportunities for solving the highly nonlinear RE for unsaturated water flow in soils.

Modellierung von Porenraumgeometrien und Transport in korngestützten porösen Medien

Poröse Medien spielen in der Hydrosphäre eine wesentliche Rolle bei der Strömung und beim Transport von Stoffen. In diesem Raum finden komplexe Prozesse statt: Advektion, Kon-vektion, Diffusion, hydromechanische Dispersion, Sorption, Komplexierung, Ionenaustausch und Abbau. Die strömungsmechanischen- und die Transportverhältnisse in porösen Medien werden direkt durch die Geometrie des Porenraumes selbst und durch die Eigenschaften der transportierten (oder strömenden) Medien bestimmt. In der Praxis wird eine Vielzahl von empirischen Modellen verwendet, die die Eigenschaften des porösen Mediums in repräsentativen Elementarvolumen wiedergeben. Die Ermittlung der in empirischen Modellen verwendeten Materialparameter erfolgt über Labor- oder Feldbestimmungsmethoden. Im Rahmen dieser Arbeit wurde das Computer-modell PoreFlow entwickelt, welches die hydraulischen Eigenschaften eines korngestützten porösen Mediums aus der mikroskopischen Modellierung des Fluidflusses und Transportes ableitet. Das poröse Modellmedium wird durch ein dreidimensionales Kugelpackungsmodell, zusam-mengesetzt aus einer beliebigen Kornverteilung, dargestellt. Im Modellporenraum wird die Strömung eines Fluids basierend auf einer stationären Lösung der Navier-Stokes-Gleichung simuliert. Die Ergebnisse der Modellsimulationen an verschiedenen Modellmedien werden mit den Ergebnissen von Säulenversuchen verglichen. Es zeigt sich eine deutliche Abhängigkeit der Strömungs- und Transportparameter von der Porenraumgeometrie sowohl in den Modell-simulationen als auch in den Säulenexperimenten.

Pore structure and column efficiency of silica monoliths in high performance liquid chromatography (HPLC)

Five different methods were critically examined to characterize the pore structure of the silica monoliths. The mesopore characterization was performed using: a) the classical BJH method of nitrogen sorption data, which showed overestimated values in the mesopore distribution and was improved by using the NLDFT method, b) the ISEC method implementing the PPM and PNM models, which were especially developed for monolithic silicas, that contrary to the particulate supports, demonstrate the two inflection points in the ISEC curve, enabling the calculation of pore connectivity, a measure for the mass transfer kinetics in the mesopore network, c) the mercury porosimetry using a new recommended mercury contact angle values. rnThe results of the characterization of mesopores of monolithic silica columns by the three methods indicated that all methods were useful with respect to the pore size distribution by volume, but only the ISEC method with implemented PPM and PNM models gave the average pore size and distribution based on the number average and the pore connectivity values.rnThe characterization of the flow-through pore was performed by two different methods: a) the mercury porosimetry, which was used not only for average flow-through pore value estimation, but also the assessment of entrapment. It was found that the mass transfer from the flow-through pores to mesopores was not hindered in case of small sized flow-through pores with a narrow distribution, b) the liquid penetration where the average flow-through pore values were obtained via existing equations and improved by the additional methods developed according to Hagen-Poiseuille rules. The result was that not the flow-through pore size influences the column bock pressure, but the surface area to volume ratio of silica skeleton is most decisive. Thus the monolith with lowest ratio values will be the most permeable. rnThe flow-through pore characterization results obtained by mercury porosimetry and liquid permeability were compared with the ones from imaging and image analysis. All named methods enable a reliable characterization of the flow-through pore diameters for the monolithic silica columns, but special care should be taken about the chosen theoretical model.rnThe measured pore characterization parameters were then linked with the mass transfer properties of monolithic silica columns. As indicated by the ISEC results, no restrictions in mass transfer resistance were noticed in mesopores due to their high connectivity. The mercury porosimetry results also gave evidence that no restrictions occur for mass transfer from flow-through pores to mesopores in the small scaled silica monoliths with narrow distribution. rnThe prediction of the optimum regimes of the pore structural parameters for the given target parameters in HPLC separations was performed. It was found that a low mass transfer resistance in the mesopore volume is achieved when the nominal diameter of the number average size distribution of the mesopores is appr. an order of magnitude larger that the molecular radius of the analyte. The effective diffusion coefficient of an analyte molecule in the mesopore volume is strongly dependent on the value of the nominal pore diameter of the number averaged pore size distribution. The mesopore size has to be adapted to the molecular size of the analyte, in particular for peptides and proteins. rnThe study on flow-through pores of silica monoliths demonstrated that the surface to volume of the skeletons ratio and external porosity are decisive for the column efficiency. The latter is independent from the flow-through pore diameter. The flow-through pore characteristics by direct and indirect approaches were assessed and theoretical column efficiency curves were derived. The study showed that next to the surface to volume ratio, the total porosity and its distribution of the flow-through pores and mesopores have a substantial effect on the column plate number, especially as the extent of adsorption increases. The column efficiency is increasing with decreasing flow through pore diameter, decreasing with external porosity, and increasing with total porosity. Though this tendency has a limit due to heterogeneity of the studied monolithic samples. We found that the maximum efficiency of the studied monolithic research columns could be reached at a skeleton diameter of ~ 0.5 µm. Furthermore when the intention is to maximize the column efficiency, more homogeneous monoliths should be prepared.rn

Imaging and modeling of pore scale processes in porous media using X-ray computed tomography and lattice Boltzmann solver

In der Erdöl– und Gasindustrie sind bildgebende Verfahren und Simulationen auf der Porenskala im Begriff Routineanwendungen zu werden. Ihr weiteres Potential lässt sich im Umweltbereich anwenden, wie z.B. für den Transport und Verbleib von Schadstoffen im Untergrund, die Speicherung von Kohlendioxid und dem natürlichen Abbau von Schadstoffen in Böden. Mit der Röntgen-Computertomografie (XCT) steht ein zerstörungsfreies 3D bildgebendes Verfahren zur Verfügung, das auch häufig für die Untersuchung der internen Struktur geologischer Proben herangezogen wird. Das erste Ziel dieser Dissertation war die Implementierung einer Bildverarbeitungstechnik, die die Strahlenaufhärtung der Röntgen-Computertomografie beseitigt und den Segmentierungsprozess dessen Daten vereinfacht. Das zweite Ziel dieser Arbeit untersuchte die kombinierten Effekte von Porenraumcharakteristika, Porentortuosität, sowie die Strömungssimulation und Transportmodellierung in Porenräumen mit der Gitter-Boltzmann-Methode. In einer zylindrischen geologischen Probe war die Position jeder Phase auf Grundlage der Beobachtung durch das Vorhandensein der Strahlenaufhärtung in den rekonstruierten Bildern, das eine radiale Funktion vom Probenrand zum Zentrum darstellt, extrahierbar und die unterschiedlichen Phasen ließen sich automatisch segmentieren. Weiterhin wurden Strahlungsaufhärtungeffekte von beliebig geformten Objekten durch einen Oberflächenanpassungsalgorithmus korrigiert. Die Methode der „least square support vector machine” (LSSVM) ist durch einen modularen Aufbau charakterisiert und ist sehr gut für die Erkennung und Klassifizierung von Mustern geeignet. Aus diesem Grund wurde die Methode der LSSVM als pixelbasierte Klassifikationsmethode implementiert. Dieser Algorithmus ist in der Lage komplexe geologische Proben korrekt zu klassifizieren, benötigt für den Fall aber längere Rechenzeiten, so dass mehrdimensionale Trainingsdatensätze verwendet werden müssen. Die Dynamik von den unmischbaren Phasen Luft und Wasser wird durch eine Kombination von Porenmorphologie und Gitter Boltzmann Methode für Drainage und Imbibition Prozessen in 3D Datensätzen von Böden, die durch synchrotron-basierte XCT gewonnen wurden, untersucht. Obwohl die Porenmorphologie eine einfache Methode ist Kugeln in den verfügbaren Porenraum einzupassen, kann sie dennoch die komplexe kapillare Hysterese als eine Funktion der Wassersättigung erklären. Eine Hysterese ist für den Kapillardruck und die hydraulische Leitfähigkeit beobachtet worden, welche durch die hauptsächlich verbundenen Porennetzwerke und der verfügbaren Porenraumgrößenverteilung verursacht sind. Die hydraulische Konduktivität ist eine Funktion des Wassersättigungslevels und wird mit einer makroskopischen Berechnung empirischer Modelle verglichen. Die Daten stimmen vor allem für hohe Wassersättigungen gut überein. Um die Gegenwart von Krankheitserregern im Grundwasser und Abwässern vorhersagen zu können, wurde in einem Bodenaggregat der Einfluss von Korngröße, Porengeometrie und Fluidflussgeschwindigkeit z.B. mit dem Mikroorganismus Escherichia coli studiert. Die asymmetrischen und langschweifigen Durchbruchskurven, besonders bei höheren Wassersättigungen, wurden durch dispersiven Transport aufgrund des verbundenen Porennetzwerks und durch die Heterogenität des Strömungsfeldes verursacht. Es wurde beobachtet, dass die biokolloidale Verweilzeit eine Funktion des Druckgradienten als auch der Kolloidgröße ist. Unsere Modellierungsergebnisse stimmen sehr gut mit den bereits veröffentlichten Daten überein.

Size-frequency distribution of boulders ≥7 m on comet 67P/Churyumov-Gerasimenko

Aims. We derive for the first time the size-frequency distribution of boulders on a comet, 67P/Churyumov-Gerasimenko (67P), computed from the images taken by the Rosetta/OSIRIS imaging system. We highlight the possible physical processes that lead to these boulder size distributions. Methods. We used images acquired by the OSIRIS Narrow Angle Camera, NAC, on 5 and 6 August 2014. The scale of these images (2.44−2.03 m/px) is such that boulders ≥7 m can be identified and manually extracted from the datasets with the software ArcGIS. We derived both global and localized size-frequency distributions. The three-pixel sampling detection, coupled with the favorable shadowing of the surface (observation phase angle ranging from 48° to 53°), enables unequivocally detecting boulders scattered all over the illuminated side of 67P. Results. We identify 3546 boulders larger than 7 m on the imaged surface (36.4 km2), with a global number density of nearly 100/km2 and a cumulative size-frequency distribution represented by a power-law with index of −3.6 +0.2/−0.3. The two lobes of 67P appear to have slightly different distributions, with an index of −3.5 +0.2/−0.3 for the main lobe (body) and −4.0 +0.3/−0.2 for the small lobe (head). The steeper distribution of the small lobe might be due to a more pervasive fracturing. The difference of the distribution for the connecting region (neck) is much more significant, with an index value of −2.2 +0.2/−0.2. We propose that the boulder field located in the neck area is the result of blocks falling from the contiguous Hathor cliff. The lower slope of the size-frequency distribution we see today in the neck area might be due to the concurrent processes acting on the smallest boulders, such as i) disintegration or fragmentation and vanishing through sublimation; ii) uplifting by gas drag and consequent redistribution; and iii) burial beneath a debris blanket. We also derived the cumulative size-frequency distribution per km2 of localized areas on 67P. By comparing the cumulative size-frequency distributions of similar geomorphological settings, we derived similar power-law index values. This suggests that despite the selected locations on different and often opposite sides of the comet, similar sublimation or activity processes, pit formation or collapses, as well as thermal stresses or fracturing events occurred on multiple areas of the comet, shaping its surface into the appearance we see today.

Observations of the Sensitivity of Beam Attenuation to Particle Size in a Coastal Bottom Boundary Layer

The goal of this study was to test the hypothesis that the aggregated state of natural marine particles constrains the sensitivity of optical beam attenuation to particle size. An instrumented bottom tripod was deployed at the 12-m node of the Martha's Vineyard Coastal Observatory to monitor particle size distributions, particle size-versus-settling-velocity relationships, and the beam attenuation coefficient (c(p)) in the bottom boundary layer in September 2007. An automated in situ filtration system on the tripod collected 24 direct estimates of suspended particulate mass (SPM) during each of five deployments. On a sampling interval of 5 min, data from a Sequoia Scientific LISST 100x Type B were merged with data from a digital floc camera to generate suspended particle volume size distributions spanning diameters from approximately 2 mu m to 4 cm. Diameter-dependent densities were calculated from size-versus-settling-velocity data, allowing conversion of the volume size distributions to mass distributions, which were used to estimate SPM every 5 min. Estimated SPM and measured c(p) from the LISST 100x were linearly correlated throughout the experiment, despite wide variations in particle size. The slope of the line, which is the ratio of c(p) to SPM, was 0.22 g m(-2). Individual estimates of c(p):SPM were between 0.2 and 0.4 g m(-2) for volumetric median particle diameters ranging from 10 to 150 mu m. The wide range of values in c(p):SPM in the literature likely results from three factors capable of producing factor-of-two variability in the ratio: particle size, particle composition, and the finite acceptance angle of commercial beam-transmissometers.

Clay mineraology and grain size composition of surface sediments from South Pacific Ocean

The reconstruction of low-latitude ocean-atmosphere interactions is one of the major issues of (paleo-)environmental studies. The trade winds, extending over 20° to 30° of latitude in both hemispheres, between the subtropical highs and the intertropical convergence zone, are major components of the atmospheric circulation and little is known about their long-term variability on geological time-scales, in particular in the Pacific sector. We present the modern spatial pattern of eolian-derived marine sediments in the eastern equatorial and subtropical Pacific (10°N to 25°S) as a reference data set for the interpretation of SE Pacific paleo-dust records. The terrigenous silt and clay fractions of 75 surface sediment samples have been investigated for their grain-size distribution and clay-mineral compositions, respectively, to identify their provenances and transport agents. Dust delivered to the southeast Pacific from the semi- to hyper-arid areas of Peru and Chile is rather fine-grained (4-8 µm) due to low-level transport within the southeast trade winds. Nevertheless, wind is the dominant transport agent and eolian material is the dominant terrigenous component west of the Peru-Chile Trench south of ~ 5°S. Grain-size distributions alone are insufficient to identify the eolian signal in marine sediments due to authigenic particle formation on the sub-oceanic ridges and abundant volcanic glass around the Galapagos Islands. Together with the clay-mineral compositions of the clay fraction, we have identified the dust lobe extending from the coasts of Peru and Chile onto Galapagos Rise as well as across the equator into the doldrums. Illite is a very useful parameter to identify source areas of dust in this smectite-dominated study area.

Bulk geochemistry and grain-size composition of surface sediments from the SW Atlantic

Surface sediments from the South American continental margin surrounding tbe Argentine Basin were studied with respect to bulk geochemistry (Caeo) and C ) and grain-size composition (sand/silt/clay relation and terrigenous silt grain-size distribution). The grain-size distributions of the terrigenous silt fraction were unmixed into three end members (EMs), using an end-member modelling algorithm. Three unimodal EMs appear to satisfactorily explain the variations in the data set of the grain-size distributions ofterrigenous silt. The EMs are related to sediment supply by rivers, downslope transport, winnowing, dispersal and re-deposition by currents. The bulk geochemical composition was used to trace the distribution of prominent water masses within the vertical profile. The sediments of the eastern South American continental margin are generally divided into a coarse-grained and carbonate-depleted southwestern part, and a finer-grained and carbonate-rich northeastern part. The transition of both environments is located at the position of the Brazil Malvinas Confluence (BMC). The sediments below the confluence mixing zone of the Malvinas and Brazil Currents and its extensions are characterised by high concentrations of organic carbon, low carbonate contents and high proportions of the intennediate grain-size end member. Tracing these properties, the BMC emerges as a distinct north-south striking feature centered at 52-54°W crossing the continental margin diagonally. Adjacent to this prominent feature in the southwest, the direct detrital sediment discharge of the Rio de la Plata is clearly recognised by a downslope tongue of sand and high proportions of the coarsest EM. A similar coarse grain-size composition extends further south along the continental slope. However, it displays bener sorting due to intense winnowing by the vigorous Malvinas Current. Fine-grained sedimentary deposition zones are located at the southwestern deeper part of the Rio Grande Rise and the southern abyssal Brazil Basin, both within the AABW domain. Less conspicuous winnowing/accumulation panerns are indicated north of the La Plata within the NADW level according to the continental margin topography. We demonstrate that combined bulk geochemical and grain-size properties of surface sediments, unmixed with an end-member algorithm, provide a powerful tool to reconstruct the complex interplay of sedimentology and oceanography along a time slice.

Coccoliths and carbonate grain-size compositions in sediment samples from the Mid-Atlantic Ridge

This study presents a differentiated carbonate budget for marine surface sediments from the Mid-Atlantic Ridge of the South Atlantic, with results based on carbonate grain-size composition. Upon separation into sand, silt, and clay sub-fractions, the silt grain-size distribution was measured using a SediGraph 5100. We found regionally characteristic grain-size distributions with an overall minimum at 8 µm equivalent spherical diameter (ESD). SEM observations reveal that the coarse particles (>8 µm ESD) are attributed to planktic foraminifers and their fragments, and the fine particles (<8 µm ESD) to coccoliths. On the basis of this division, the regional variation of the contribution of foraminifers and coccoliths to the carbonate budget of the sediments are calculated. Foraminifer carbonate dominates the sediments in mesotropic regions whereas coccoliths contribute most carbonate in oligotrophic regions. The grain size of the coccolith share is constant over water depth, indicating a lower susceptibility for carbonate dissolution compared to foraminifers. Finally, the characteristic grain-size distribution in fine silt (<8 µm ESD) is set into context with the coccolith assemblage counted and biometrically measured using a SEM. The coccoliths present in the silt fraction are predominantly large species (length > 4 µm). Smaller species (length < 4 µm) belong to the clay fraction (<2 µm ESD). The average length of most frequent coccolith species is connected to prominent peaks in grain-size distributions (ESD) with a shape factor. The area below Gaussian distributions fitted to these peaks is suggested as a way to quantitatively estimate the carbonate contribution of single coccolith species more precisely compared to conventional volume estimates. The quantitative division of carbonate into the fraction produced by coccoliths and that secreted by foraminifers enables a more precise estimate for source/sink relations of consumed and released CO2 in the carbon cycle. The allocation of coccolith length and grain size (ESD) suggests size windows for the separation or accumulation of distinct coccolith species in investigations that depend on non to slightly-mixed signals (e.g., isotopic studies).

Eolian grain-size record of early Paleogene sediments from DSDP Hole 22-215 and ODP Leg 208 sites

To date, the only Southern Hemisphere eolian grain-size record constructed for the early Paleogene comes from Deep Sea Drilling Project Site 215. Ten early Paleogene sediment samples from Site 215 were collected and processed to show that the existing eolian grain-size record at this site can be reproduced. Five samples each from Ocean Drilling Program Sites 1263 and 1267 were similarly examined to test the possibility of generating new Southern Hemisphere eolian grain-size records for the early Paleogene. Our results indicate that an eolian grain-size signal can be constructed at Walvis Ridge, although the record will be complicated by hemipelagic terrigenous inputs. Further, we assert that a record generated at a site located on the deep flanks of Walvis Ridge is particularly susceptible to hemipelagic influence.

Water level time series and sediment grain size model

The environment of ebb-tidal deltas between barrier island systems is characterized by a complex morphology with ebb- and flood-dominated channels, shoals and swash bars connecting the ebb-tidal delta platform to the adjacent island. These morphological features reveal characteristic surface sediment grain-size distributions and are subject to a continuous adaptation to the prevailing hydrodynamic forces. The mixed-energy tidal inlet Otzumer Balje between the East Frisian barrier islands of Langeoog and Spiekeroog in the southern North Sea has been chosen here as a model study area for the identification of relevant hydrodynamic drivers of morphology and sedimentology. We compare the effect of high-energy, wave-dominated storm conditions to mid-term, tide-dominated fair-weather conditions on tidal inlet morphology and sedimentology with a process-based numerical model. A multi-fractional approach with five grain-size fractions between 150 and 450 µm allows for the simulation of corresponding surface sediment grain-size distributions. Net sediment fluxes for distinct conditions are identified: during storm conditions, bed load sediment transport is generally onshore directed on the shallower ebb-tidal delta shoals, whereas fine-grained suspended sediment bypasses the tidal inlet by wave-driven currents. During fair weather the sediment transport mainly focuses on the inlet throat and the marginal flood channels. We show how the observed sediment grain-size distribution and the morphological response at mixed-energy tidal inlets are the result of both wave-dominated less frequent storm conditions and mid-term, tide-dominant fair-weather conditions.