Chemical and physical characterization of clay bodies

Suitable methods for the assessment of the effect of freeze-thaw action upon ceramic tiles have been determined. The results obtained have been shown to be reproducible with some work in this area still warranted. The analysis of Whichford Potteries clays via a variety of analytical techniques has shown them to be a complex mix of both clay and non-clay minerals. 57Fe Mössbauer spectroscopy has highlighted the presence of both small and large particleα-Fe203, removable via acid washing. 19F MAS NMR has demonstrated that the raw Whichford Pottery clays examined have negligible fluorine content. This is unlikely to be detrimental to ceramic wares during the heating process. A unique technique was used for the identification of fluorine in solid-state systems. The exchange of various cations into Wyoming Bentonite clay by microwave methodology did not show the appearance of five co-ordinate aluminium when examined by 27Al MAS NMR. The appearance of Qo silicate was linked to an increase in the amount of tetrahedrally bound aluminium in the silicate framework. This is formed as a result of the heating process. The analysis of two Chinese clays and two Chinese clay raw materials has highlighted a possible link between the two. These have also been shown to be a mix of both clay and non-clay minerals. Layered double hydroxides formed by conventional and microwave methods exhibited interesting characteristics. The main differences between the samples examined were not found to be solely attributable to the differences between microwave and conventional methods but more attributable to different experimental conditions used.

Phosphorus bearing minerals in iron ores and their possible benefication

Modern electron optical techniques together with X-ray and mineralogical examination have been used to study the occurrence and form of phosphorus bearing minerals in iron ores. Three ores have been studied - Bahariya and Aswan from Egypt and Frodingham ironstone from U.K. The iron in the Bahariya iron ore is mainly as hematite and goethite. The gangue minerals are halite, gypsum, barytes, quartz and calcite. Iron content is between 49.8 to 63.2% and phosphorus 0.14 to 0.34%. The phosphorus occurs as very fine particles of apatite which are distributed throughout the ore. Removal of the phosphorus would require very fine grinding followed by acid leaching. Aswan iron ore is an oolitic iron ore; the iron content between 41-57% and phosphorus content 0.1 to 2.9%. It is mainly hematitic with variable quantities of quartz, apatite and small amount of clay minerals. In the oolitic iron ore beds, apatite occurs in the hematite matrix; filling in the pores of the oolithic surfaces, or as matrix cementing the ooliths with the hematite grains. In sandstone claybeds the distribution of the apatite is mainly in the matrix. It is suggested that the liberation size for the apatite would be -80 m and flotation concentration could be applied for the removal of apatite from Aswan ore. Frodingham ironstone occurs in the lower Jurassic bed of the South Humberside area. The average iron content is 25% and the phosphorus is 0.32%. Seven mineral phases were identified by X-ray; calcite, quartz, chamosite, hematite, siderite, apatite, and chlorite. Apatite occurs as very fine grains in the hematite and chamosite ooliths; as matrix of fine grains intergrown with chamosite and calcite grains; and as anhedral and sub rounded grains in the ooliths (8-28 m). It is suggested that two processes are possible for the dephosphorisation; the Flox process or a reduction roast followed by fine grinding, magnetic separation, and acid leaching.

(Table 1) Clay and non-clay mineral composition of dirty ice samples from across the Arctic

Extensive dirty ice patches with up to 7 kg/m**2 sediment concentrations in layers of up to 10 cm thickness were encountered in 2005 and 2007 in numerous areas across the central Arctic. The Fe grain fingerprint determination of sources for these sampled dirty ice floes indicated both Russian and Canadian sources, with the latter dominating. The presence of benthic shells and sea weeds along with thick layers (2-10 cm) of sediment covering 5-10 m2 indicates an anchor ice entrainment origin as opposed to suspension freezing for some of these floes. The anchor ice origin might explain the dominance of Canadian sources where only narrow flaw leads occur that would not favor suspension freezing as an entrainment process. Expandable clays, commonly used as an indicator of a Kara Sea origin for dirty sea ice, are present in moderately high percentages (>20%) in many circum-Arctic source areas, including the Arctic coasts of North America. Some differences between the Russian and the North American coastal areas are found in clay mineral abundance, primarily the much higher abundance of chlorite in North America and the northern Barents Sea as opposed to the rest of the Russian Arctic. However, sea ice clay mineralogy matched many source areas, making it difficult to use as a provenance tool by itself. The bulk mineralogy (clay and non-clay) does not match specific sources possibly due to reworking of the sediment in dirty floes through summer melting or the failure to characterize all possible source areas.

(Table 1) Peak intensity of minerals in ODP Hole 126-793B

Sediments and rocks recovered during Ocean Drilling Program Leg 126 at Sites 792 and 793 in the Izu-Bonin forearc basin are described with a primary focus on clay mineralogy. Evidence for diagenetic hydrothermal alteration processes is present in the upper Oligocene to lower Miocene sediments at these sites. The vitric and pumiceous sand/sandstone and pumiceous gravel contain high concentrations of smectites, zeolites, and gypsum. Microscopic observations show that the volcanic glass and feldspars have been altered to smectites and zeolites. The authigenic mineral assemblages indicate that these minerals resulted from precipitation from circulating fluids, as well as from the alteration of glass and feldspar under temperature conditions that may have reached 200°-300°C. Mineral assemblages in microfractures display thermal gradients that possibly reflect cooling effects.

(Table 1) Sample locations and clay mineral data of sediment surface samples from the Barents Sea region

A new surface sediment sample set gained in the western Barents Sea by the MAREANO program has been analysed for basic clay mineral assemblages. Distribution maps including additional samples from earlier German research cruises to and off Svalbard are compiled. Some trends in the clay mineral assemblages are related to the sub-Barents Sea geology because the Quaternary sediment cover is rather thin. Additionally, land masses like Svalbard and northern Scandinavia dominate the clay mineral signal with their erosional products. Dense bottom water, very often of brine origin, that flows within deep troughs, such as the Storfjorden or Bear Island Trough, transport the clay mineral signal from their origin to the Norwegian-Greenland Sea.

(Table T1) Mineral composition of oriented clay aggregates from ODP Leg 190 sites

Three sites were cored on the landward slope of the Nankai margin of southwest Japan during Leg 190 of the Ocean Drilling Program. Sites 1175 and 1176 are located in a trench-slope basin that was constructed during the early Pleistocene (~1 Ma) by frontal offscraping of coarse-grained trench-wedge deposits. Rapid uplift elevated the substrate above the calcite compensation depth and rerouted a transverse canyon-channel system that had delivered most of the trench sediment during the late Pliocene (1.06-1.95 Ma). The basin's depth is now ~3000 to 3020 m below sea level. Clay-sized detritus (<2 µm) did not change significantly in composition during the transition from trench-floor to slope-basin environment. Relative mineral abundances for the two slope-basin sites average 36-37 wt% illite, 25 wt% smectite, 22-24 wt% chlorite, and 15-16 wt% quartz. Site 1178 is located higher up the landward slope at a water depth of 1741 m, ~70 km from the present-day deformation front. There is a pronounced discontinuity ~200 m below seafloor between muddy slope-apron deposits (Quaternary-late Miocene) and sandier trench-wedge deposits (late Miocene; 6.8-9.63 Ma). Clay minerals change downsection from an illite-chlorite assemblage (similar to Sites 1175 and 1176) to one that contains substantial amounts of smectite (average = 45 wt% of the clay-sized fraction; maximum = 76 wt%). Mixing in the water column homogenizes fine-grained suspended sediment eroded from the Izu-Bonin volcanic arc, the Izu-Honshu collision zone, and the Outer Zone of Kyushu and Shikoku, but the spatial balance among those contributors has shifted through time. Closure of the Central America Seaway at ~3 Ma was particularly important because it triggered intensification of the Kuroshio Current. With stronger and deeper flow of surface water toward the northeast, the flux of smectite from the Izu-Bonin volcanic arc was dampened and more detrital illite and chlorite were transported into the Shikoku-Nankai system from the Outer Zone of Japan.

Clay mineralogy of ODP Leg 178 sites

The clay mineral compositions of upper Miocene to Quaternary sediments recovered at Ocean Drilling Program (ODP) Leg 178, Sites 1095 and 1096, from the continental rise west of the Antarctic Peninsula were analyzed in order to reconstruct the Neogene and Quaternary Antarctic paleoclimate and ice dynamics. The clay mineral assemblages are dominated by smectite, illite, and chlorite. Kaolinite occurs only in trace amounts. Analysis of a surface-sample data set facilitates the assignment of these clay minerals to particular source areas on the Antarctic Peninsula and, thus, the reconstruction of transport pathways. In the ODP cores, clay mineral composition cyclically alternates between two end-member assemblages. One assemblage is characterized by <20% smectite and >40% chlorite. The other assemblage has >20% smectite and <40% chlorite. Illite fluctuates between 30% and 50% without a significant affinity to one end-member assemblage. By comparison with a Quaternary sediment sequence from gravity core PS1565, the clay mineral fluctuations can be ascribed to glacial and interglacial periods, respectively. The cyclic changes in the clay mineral composition suggest that glacial-interglacial cycles, repeated ice advances and retreats, and changes in the Antarctic ice volume were already a main control of the global climate in late Miocene time. Throughout the late Neogene and Quaternary, the clay mineral records in the drift sediments exhibit only slight long-term changes predominantly attributed to local changes in glacial erosion and supply of source rocks. The absence of clear long-term trends associated with major climatic or glaciological changes points to an onset of vast glaciation in the Antarctic Peninsula region before ~9 Ma and to relative stability of the Antarctic ice sheet since then.

Clay-mineral composition and biogenic opal content of Late Neogene to Quaternary sediments of the Antarctic Peninsula region

Clay-mineral composition and biogenic opal content in upper Miocene to Quaternary drift sediments recovered at two Ocean Drilling Program (ODP) sites from the continental rise in the Bellingshausen Sea had been analyzed in order to reconstruct the climatic and glacial history of the Antarctic Peninsula. The clay mineral composition at both sites is dominated by smectite, illite, and chlorite, and alternates between a smectite-enriched and a chlorite-enriched assemblage throughout the last 9.3 my. The spatial distribution of clay minerals in Holocene sediments west of the Antarctic Peninsula facilitates the identification of particular source areas, and thus the reconstruction of transport pathways. The similarity to clay mineral variations reported from upper Quaternary sequences suggests that the short-term clay-mineralogical fluctuations in the ODP cores reflect glacial-interglacial cyclicity. Thus, repeated ice advances and retreats in response to a varying size of the Antarctic Peninsula ice cap are likely to have occurred throughout the late Neogene and Quaternary. The clay minerals in the drift sediments exhibit only slight long-term variations, which are caused by local changes in glacial erosion and in supply of source rocks, rather than by major climatic changes. The opal records at the ODP sites are dominated by long-term variations since the late Miocene. We infer that the opal content in the drift sediments, although it is influenced by dissolution in the water column and the sediment column and by the burial with lithogenic detritus, provides a signal of paleoproductivity. Because the annual sea-ice coverage is regarded as the main factor controlling biological productivity, the opal signal helps to reconstruct paleoceanographic changes in the Bellingshausen Sea. Slightly enhanced opal deposition during the late Miocene indicates slightly warmer climatic conditions in the Antarctic Peninsula area than at present. During the early Pliocene, enhanced opal deposition in the Pacific sector of the Southern Ocean and coinciding high opal concentrations in sedimentary sequences from the Atlantic and Indian sectors document a strong reduction of sea-ice cover and relatively warm climatic conditions. Thereby, the early onset of the Pliocene warmth in the Bellingshausen Sea points to a positive feedback of regional Antarctic climate on the global thermohaline circulation. A decrease of opal deposition between 3.1 and 2.6 Ma likely reflects sea-ice expansion in response to reduced supply of northern-sourced deep-waters to the Southern Ocean, caused by the onset of Northern Hemisphere glaciation. Throughout the Quaternary, a relatively constant level of opal deposition on the Antarctic continental margin indicates relatively stable climatic conditions.

Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas

ALVES, Ana paula Melo. Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas. 2009. 124 f. Tese (Doutorado em Quimica) - Centro de Ciências Exatas e da Natureza, Universidade Federal da Paraíba, João Pessoa, PB, 2009.

Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas

ALVES, Ana paula Melo. Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas. 2009. 124 f. Tese (Doutorado em Quimica) - Centro de Ciências Exatas e da Natureza, Universidade Federal da Paraíba, João Pessoa, PB, 2009.

Low temperature synthesis of zeolite N from kaolinites and montmorillonites

Zeolite N was produced from a variety of kaolinites and montmorillonites at low temperature (b100 °C) in a constantly stirred reactor using potassic and potassic+sodic mother liquors with chloride or hydroxyl anions. Reactions were complete (N95% product) in less than 20 h depending on initial batch composition and type of clay minerals. Zeolite N with 1.0bSi/Alb2.2 was produced under these conditions using KOH in the presence of KCl, NaCl, KCl+NaCl and KCl+NaOH. Zeolite N was also formed under high potassium molarities in the absence of KCl. Zeolite synthesis was more sensitive to water content and temperature when sodium was used in initial batch compositions. Syntheses of zeolite N by these methods were undertaken at bench, pilot and industrial scales.

Soil Carbon Turnover Measurement by Physical Fractionation at a Forest-to-Pasture Chronosequence in the Brazilian Amazon

The effect of conversion from forest-to-pasture upon soil carbon stocks has been intensively discussed, but few studies focus on how this land-use change affects carbon (C) distribution across soil fractions in the Amazon basin. We investigated this in the 20 cm depth along a chronosequence of sites from native forest to three successively older pastures. We performed a physicochemical fractionation of bulk soil samples to better understand the mechanisms by which soil C is stabilized and evaluate the contribution of each C fraction to total soil C. Additionally, we used a two-pool model to estimate the mean residence time (MRT) for the slow and active pool C in each fraction. Soil C increased with conversion from forest-to-pasture in the particulate organic matter (> 250 mu m), microaggregate (53-250 mu m), and d-clay (< 2 mu m) fractions. The microaggregate comprised the highest soil C content after the conversion from forest-to-pasture. The C content of the d-silt fraction decreased with time since conversion to pasture. Forest-derived C remained in all fractions with the highest concentration in the finest fractions, with the largest proportion of forest-derived soil C associated with clay minerals. Results from this work indicate that microaggregate formation is sensitive to changes in management and might serve as an indicator for management-induced soil carbon changes, and the soil C changes in the fractions are dependent on soil texture.

Synthesis and characterisation of layered double hydroxides and their application for water purification

Layered doubly hydroxides (LDHs) also known as hydrotalcites or anionic clays are a group of clay minerals that have shown promise for the removal of toxic anions from water through both anion exchange and a process known as the reformation effect. This project has involved the preparation and characterisation of LDH materials as well as the investigation of their ability to remove selected anions from aqueous solutions by the reformation effect. The LDH materials were successfully prepared from magnesium, aluminium, zinc and chromium chloride salts using the co-precipitation method. Samples were characterised using powder X-ray diffraction (XRD) and thermogravimetry (TG) to confirm the presence of LDHs. Powder XRD revealed a characteristic LDH structure for all LDH samples. Thermal Analysis showed decomposition usual occurred through a three or four step process as expected for LDHs. Preliminary investigations of the removal of sulfate, nitrate and fluoride by an Mg/Al LDH were carried out, and the products were characterised using XRD and TG which showed that an LDH material similar to the original hydrotalcite was formed after reformation. A Zn/Al LDH was investigated as a potential sorbent material for the removal of iodine and iodide from water. It was found that the LDH was a suitable adsorbent which is able to remove almost all of the iodine present in the test solutions. Again, the products were characterised by XRD, TG and evolved gas mass spectrometry (EGMS) in an attempt to better understand the iodine removal process. Powder XRD showed successful reformation of the LDH structure and TG/EGMS showed that only a small amount of iodine species were lost during thermal decomposition. Finally, the mineral stichtite a Mg/Cr LDH was successfully synthesised and investigated using XRD, TG and EGMS. Unfortunately, due to lack of time it was not possible to identify any new uses for the mineral stichtite in the current project.