Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

SUBSTRATE, LIME, PHOSPHORUS AND TOPDRESS FERTILIZATION IN MACAW PALM SEEDLING PRODUCTION

ABSTRACT The macaw palm [Acrocomia aculeata (Jacq.) Lood. ex Mart] has been domesticated to subsidize biodiesel production programs in Brazil. However, little is known about the seedling production of this species. This study aimed to evaluate substrate mixtures, limestone and phosphorus rates for substrate amendment and topdressing frequency in macaw palm seedlings. Three trials were conducted in a greenhouse up to six months of nursery cultivation. Trial 1: determination of percent mineral and organic fractions of seven substrate mixtures. Trial 2: evaluation of four limerates for soil amendment versus four phosphorus rates. Trial 3: evaluation of N, K and Mg topdressing frequency. Significant differences were found in the three trials for most of the variables (plant height, leaf number, shoot dry mass, root dry mass, vigor and bulb diameter). The main results obtained were as follow: Trial1 - the best seedling growth was observed in substrates with at least 25% organic matter. Trial2 -lime rates ranging from 0.50 to 1.25 kg associated with 3 to 4 kg of single superphosphate per m3 of substrate provided the best seedling growth. Trial 3 - topdressing fertilization provided better development of seedlings regardless of frequency.

Combustion properties of biomass residues rich in phosphorus

Tillgången på traditionella biobränslen är begränsad och därför behöver man ta fram nya, tidigare outnyttjade biobränslen för att möta de uppställda CO2 emissionsmålen av EU och det ständigt ökande energibehovet. Under de senare åren har intresset riktats mot termisk energiutvinning ur olika restfraktioner och avfall. Vid produktion av fordonsbränsle ur biomassa är den fasta restprodukten ofta den största procesströmmen i produktionsanläggningen. En riktig hantering av restprodukterna skulle göra produktionen mera lönsam och mer ekologiskt hållbar. Ett alternativ är att genom förbränning producera elektricitet och/eller värme eftersom dessa restprodukter anses som CO2-neutrala. Målsättningen med den här avhandlingen var att studera förbränningsegenskaperna hos några fasta restprodukter som uppstår vid framställning av förnybara fordonsbränslen. De fyra undersökta materialen är rapskaka, palmkärnskaka, torkad drank och stabiliserat rötslam. I studien används ett stort urval av undersökningsmetoder, från laboratorieskala till fullskalig förbränning, för att identifiera de huvudsakliga utmaningarna förknippade med förbränning av restprodukterna i pannor med fluidiserad bäddteknik. Med hjälp av detaljerad bränslekarakterisering kunde restprodukterna konstateras vara en värdefull källa för värme- och elproduktion. Den kemiska sammansättningen av restprodukterna varierar stort jämfört med mera traditionellt använda biobränslen. En gemensam faktor för alla de studerade restprodukterna är en hög fosforhalt. På grund av de låga fosforkoncentrationerna i de traditionella biobränslena har grundämnet hittills inte ansetts spela någon större roll i askkemin. Experimenten visade nu att fosfor inte mera kan försummas då man studerar kemin i förbränningsprocesser, då allt flera fosforrika bränslen tränger in på energimarknaden.

Treatment of NI-containing acidic mine waters with calcite side-stones

Acid mine drainage (AMD) presents a serious problem for the environment for the massive formation of acidic leachates containing heavy metals. The present work deals with the AMD treatment using neutralizing limestone side-products. The conventional methods for prevention, mitigating and control of AMD formation are described. The experimental testing of Nordkalk Oy calcite-containing side-stones for acid neutralizing and removal of nickel from solutions presents the research objective. The batch experiments in acid neutralizing with subsequent metal content analysis were carried out. The results showed the dependence of pH on the dose of neutralizing material and the exposure time. The nickel removal, unlike iron, within the pH range from 1.2 to 6.0 appeared to be inadequate. The further research on nickel co-precipitation with iron and aluminium may appear to be necessary together with testing of alkalinity strengthening materials.

Treatment of Fe-containing Acid Mine Waters in Fixed Bed Adsorption Column with Calcite Side-Stone

The acid mining drainage is considered the most significant environmental pollution problem around the world for the extensive formation acidic leachates containing heavy metals. Adsorption is widely used methods in water treatment due to it easy operation and the availability of a wide variety of commercial adsorbent (low cost). The primary goal of this thesis was to investigate the efficiency of neutralizing agents, CaCO3 and CaSiO3, and metal adsorption materials with unmodified limestone from Company Nordkalk Oy. In addition to this, the side materials of limestone mining were tested for iron adsorption from acidic model solution. This study was executed at Lappeenranta University of Technology, Finland. The work utilised fixed-bed adsorption column as the main equipment and large fluidized column. Atomic absorption spectroscopy (AAS) and x-ray diffraction (XRD) was used to determine ferric removal and the composition of material respectively. The results suggest a high potential for the studied materials to be used a low cost adsorbents in acid mine drainage treatment. From the two studied adsorbents, the FS material was more suitable than the Gotland material. Based on the findings, it is recommended that further studies might include detailed analysis of Gotland materials.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Drift dispersal in central Southern Ontario /

Two tills are readily identi-f i able in central Southern Ontario, a very stony, loose deposit o-f variable matrix (Dummer till) and a moderately stony, fissile and compact deposit that is more homogeneous (drumlinized till). The quantity o-f Precambr i an, Paleozoic and Shadow Lake Formation (Paleozoic) rock types were determined and corresponding isopleth maps drawn. The changes in lithology content occurred in the direction o-f transport, there-fore, compositional isopleths o-f till may be considered equipotential lines for the reconstruction of glacier flow paths. Areal gradations of drift lithology indicated that the prime agents of dispersal were ice and glacial meltwaters. The down-ice abundance trend of till components indicated a dispersal pattern showing the concentration of a given lithology type peaking within a few kilometres of the source followed by a rapid decline and thereafter, a more gradual decrease with increasing distance. Within the esker deposits, igneous rocks may form the major component and can extend further onto the limestone plain than in the adjacent till. Evidence is presented that indicates the "style" of dispersal was one in which glacial ice may have been strongly influenced by local bedrock topography and the regional structural trends. The ice tended to follow pre-existing valleys and lows, depositing till composed mainly of local bedrock. Gradations in Paleozoic clast content showed that the local bedrock lithology became the primary till component within 3 km of down-ice transport. Evidence is presented that indicated the last glaciation may have occurred as a relatively thin ice mass, followed by stagnation and recession. No evidence of a lateglacial re-advance was found within the study area. Because of the lack of a contact between the Dummer and drumlinized till, and because of results showing gradation of the Dummer till into the drumlinized till (as indicated by lithology content and grain size), it is suggested that no re-advance occurred.

Geology of the Gander Group, Gander River Ultramafic Belt and Davidsville Group in the Jonathan's Pond - Weir's Pond Area, northeast Newfoundland /

The study area is situated in NE Newfoundland between Gander Lake and the north coast and on the boundary between the Gander and Botwood tectonostratigraphic zones (Williams et al., 1974). The area is underlain by three NE trending units; the Gander Group, the Gander River Ultramafic Belt (the GRUB) and the Davidsville Group. The easternmost Gander Group consists of a thick, psammitic unit composed predominantly of psammitic schist and a thinner, mixed unit of semipelitic and pelitic schist with minor psammite. The mixed unit may stratigraphically overlie the psammitic unit or be a lateral facies equivalent of the latter. No fossils have been recovered from the Gander Group. The GRUB is a terrain of mafic and ultramafic plutonic rocks with minor pillow lava and plagiogranite. It is interpreted to be a dismembered ophiolite in thrust contact with the Gander Group. The westernmost Davidsville Group consists of a basal conglomerate, believed deposited unconformably upon the GRUB from which it was derived, and an upper unit of greywacke and slate, mostly of turbidite origin, with minor limestone and calcareous sandstone. The limestone, which lies near the base of the unit, contains Upper Llanvirn to Lower Llandeilo fossils. The Gander and Davidsville Groups display distinctly different sedimentological , structural and metamorphic histories. The Gander Group consists of quartz-rich, relatively mature sediment. It has suffered three pre-Llanvirn deformations, of which the main deformation, Dp produced a major, NE-N-facing recumbent anticline in the southern part of the study area. Middle greenschist conditions existed from D^ to D- with growth of metamorphic minerals during each dynamic and static phase. In contrast, the mineralogically immature Davidsville Group sediment contains abundant mafic and ultramafic detritus which is absent from the Gander Group. The Davidsville Group displays the effects of a single penetrative deformation with localized D_ and D_ features, all of which can be shown to postdate D_ in the Gander Group. Rotation of the flat Gander S- into a subvertical orientation near the contact with the GRUB and the Davidsville Group is believed to be a Davidsville D^ feature. Regional metamorphism in the Davidsville Group is lower greenschist with a single growth phase, MS . These sedimentological, structural and metamorphic differences between the Gander and Davidsville Groups persist even where the GRUB is absent and the two units are in contact, indicating that the tectonic histories of the Gander and Davidsville Groups are distinctly different. Structural features in the GRUB, locally the result of multiple deformations, may be the result of Gander and/or Davidsville deformations. Metamorphism is in the greenschist facies. Geochemical analyses of the pillow lava suggest that these rocks were formed in a back-arc basin. Mafic intrusives in the Gander Group appear to be the result of magraatism separate from that producing the pillow lava. The Gander Group is interpreted to be a continental rise prism deposited on the eastern margin of the Late Precambrian-Lower Paleozoic lapetus Ocean. The GRUB, oceanic crust possibly formed in a marginal basin to the west, is believed to have been thrust eastward over the Gander Group, deforming the latter, during the pre-Llanvirnian, possibly Precambrian, Ganderian Orogeny. The Middle Ordovician and younger Davidsville Group was derived from, and deposited unconformably on, this deformed terrain. Deformation of the Davidsville Group occurred during the Middle Devonian Acadian Orogeny.

Structural, stratigraphic and geochemical studies of the Horwood Peninsula - Gander Bay Area, Northeast Newfoundland /

The Horwood Peninsula - Gander Bay area is located at NE Newfoundland in the Botwood Zone (Williams et a1., 1974) or in the Dunnage Zone (Williams, 1979) of the Central Mobile Belt of the Newfoundland Appalachians. The area is underlain by Middle Ordovician to possible Lower Silurian rocks of the Davidsville and Indian Islands Groups, respectively. Three conformable formations named informally : the Mafic Volcanic Formation, the Greywacke and Siltstone Formation and the Black Slate Formation, have been recognized in the Davidsville Group. The Greywacke and the Black Slate Formations pass locally into a Melange Formation. From consideration of regional structure and abundant locally-derived mafic volcanic olisto- 1iths in the melange, it is considered to have originated by gravity sliding rather than thrusting. Four formations have been recognized in the Indian Islands Group. They mainly contain silty slate and phyllite, grey cherty siltstone, green to red micaceous siltstone and limestone horizons. Repetition of lithological units by F1 folding are well-demonstrated in one of formations in this Group. The major structure in this Group on the Horwood Peninsula is interpreted to be a synclinal complex. The lithology of this Group is different from the Botwood Group to the west and is probably Late Ordovician and/or Early Silurian in age. The effects of soft-sediment deformation can be seen from the lower part of the Davidsville Group to the middle part of the Indian Islands Group indicating continuous and/or episodic slumping and sliding activities throughout the whole area. However, no siginificant depOSitional and tectonic break that could be assigned to the Taconian Orogeny has been recognized in this study. Three periods of tectonic deformation were produced by the Acadian Orogeny. Double boudinage in thin dikes indicates a southeast-northwest sub-horizontal compression and main northeast-southwest sub-horizontal extension during the D1 deformation. A penetrative, axial planar slaty cleavage (Sl) and tight to isocJ.ina1 F1 folds are products of this deformation. The D2 and D3 deformations formed S2 and S3 fabrics associated with crenulations and kink bands which are well-shown in the slates and phyllites of the Indian Islands Group. The D2 and D3 deformations are the products of vertical and northeast-southwest horizontal shortening respectively. The inferred fault between the Ordovician slates (Davidsville Group) and the siltstones (Indian Islands Group) suggested by Williams (1963, 1964b, 1972, 1978) is absent. Formations can be followed without displacement across this inferred fault. Chemically, the pillow lavas, mafic agglomerates, tuff beds and diabase dikes are subdivided into three rock suites : (a) basaltic komatiite (Beaver Cove Assemblage), (b) tholeiitic basalt (diabase dikes), (c) alkaline basalt (Shoal Bay Assemblage). The high Ti02 , MgO, Ni contents and bimodal characteristic of the basaltic komatiite in the area are comparable to the Svartenhuk Peninsula at Baffin Bay and are interpreted to be the result of an abortive volcano-tectonic rift-zone in a rear-arc basin. Modal and chemical analyses of greywackes and siltstones show the trend of maturity of these rocks increasing from poorly sorted Ordovician greywackes to fairly well-sorted Silurian siltstones. Rock fragments in greywackes indicate source areas consisting of plagiogranite, low grade metamorphic rocks and ultramafic rocks. Rare sedimentary structures in both Groups indicate a southeasterly provenance. Trace element analyses of greywackes also reveal a possible island-arc affinity.

Feeding rates, parental investment, and brood reduction in Caspian terns (Sterna caspia)

Fresh egg-weights and feeding rates to chicks were related to chick survival as one means of quantifying apportionment of parental investment wi thin broods of Caspian Terns (SterDI casRla) at a colony in Georgian Bay. Lake Huron, during 1978 and 1979. Ftrst-laid eggs from 2-egg clutches were Significantly heavier and usually hatched one to three days earlier than second-laid eggs in both years of the study. In both years, first-hatched chicks were larger and generally better fed than second-hatched siblings. The disparity between feedIng rates of first- and second-hatched ehicks was greater in 1979. Brood feeding I rates correlated positively with the percentage of food fed to the least-fed sibUng through the period of B-chick ages zero to 10 days in 1978. I suggest that after this age period, parental control over whlcb cbick was fed diminished. In 1978, 10 of 16 secondhatched chicks were fed more than their older siblings during their first 5 days. 'lb.is is interpreted as a parental response to reduce the competitive advantage of the larger first-hatched chicks. Most chick losses were apparently caused by starvation or preda. tion. In 1979, seeorvl-hatched chick disappearance (due to predation) was -related to low feeding rates, whereas first-hatched chick disappearance was related to low fresh egg-weights.. First-hatched chicks survived better than second-hatched chicks both years, and more pairs fledged two chicks in 1978. Maximum estimated feeding rates at the nest and fledging ages suggested that food was more avatlable in 1978 than in 1979. In 1979, second eggs apparently functioned as "insurance" eggs. When the first-laid egg falled to hatch, or the first-hatched chick died, the second-hatched chick was often successfully fledged. When first-hatched chicks survived, the second-hatched chick usually starved or was preyed upon, reducing the brood to one chick. Parental investment patterns favored first-hatched chicks. Brood reduction, when employed, discouraged total nest failure, however, under appropriate conditions, brood reduction was avoided and full broods (or two chicks) were fledged.

The sedimentology of the lower Silurian whirlpool sandstone in subsurface Lake Erie, Ontario

The lower Silurian Whirlpool Sandstone is composed of two main units: a fluvial unit and an estuarine to transitional marine unit. The lowermost unit is made up of sandy braided fluvial deposits, in shallow valleys, that flowed towards the northwest. The fluvial channels are largely filled by cross-bedded, well sorted, quartzose sands, with little ripple crosslaminated or overbank shales. Erosionally overlying this lower unit are brackish water to marine deposits. In the east, this unit consists of estuarine channels and tidal flat deposits. The channels consist of fluvial sands at the base, changing upwards into brackish and tidally influenced channelized sandstones and shales. The estuarine channels flowed to the southwest. Westwards, the unit contains backbarrier facies with extensive washover deposits. Separating the backbarrier facies from shoreface sandstone facies to the west, are barrier island sands represented by barrier-foreshore facies. The barrier islands are dissected by tidal inlets characterized by fining upward abandonment sequences. Inlet deposits are also present west of the barrier island, abandoned by transgression on the shoreface. The sandy marine deposits are replaced to the west by carbonates of the Manitoulin Limestone. During the latest Ordovician, a hiatus in crustal loading during the Taconic Orogeny led to erosional offloading and crustal rebound, the eroded material distributed towards the west, northwest and north as the terrestrial deposits of the fluvial Whirlpool. The "anti-peripheral bulge" of the rebound interfered with the peripheral bulge of the Michigan Basin, nulling the Algonquin Arch, and allowing the detritus of the fluvial Whirlpool to spread onto the Algonquin Arch. The Taconic Orogeny resumed in the earliest Silurian with crustal loading to the south and southeast, and causing tilting of the surface slope in subsurface Lake Erie towards the ii southwest. Lowstand terrestrial deposits were scoured into the new slope. The new crustal loading also reactivated the peripheral bulge of the Appalachian Basin, allowing it to interact with the bulge of the Michigan Basin, raising the Algonquin Arch. The crustal loading depressed the Appalachian basin and allowed transgression to occur. The renewed Algonquin Arch allowed the early Silurian transgression to proceed up two slopes, one to the east and one to the west. The transgression to the east entered the lowstand valleys and created the estuarine Whirlpool. The rising arch caused progradation of the Manitoulin carbonates upon shoreface facies of the Whirlpool Sandstone and upon offshore facies of the Cabot Head Formation. Further crustal loading caused basin subsidence and rapid transgression, abandoning the Whirlpool estuary in an offshore setting.

Walker Brothers Quarries Limited fonds, 1975, 1980-1981, 1984, 1987-1989

Serving the Niagara and surrounding areas for over 120 years, Walker Industries has made its impact not only commercially, but also culturally. Beginning in 1875 with the erection of a stone sawing mill on a property John Walker purchased from the Welland Canal Loan Company. One of the first projects Walker cut stone for was the Merritton Town Hall. In 1882 the business expanded to include Walkers children, changing the name to Walker & Sons. Eventually in 1887 the two eldest sons took control of the business operation and their partnership changed the company’s name to Walker Brothers, the same year the company began operating its first quarry. The quarry was conveniently located alongside the 3rd Welland canal, offering easy access to Toronto and Hamilton. It was also close to the railway system which allowed immediate access to Thorold and Niagara Falls and later access to parts of Ontario and Quebec. The quarry supplied stone to build numerous halls and armouries across Ontario. A use was also found for the ‘waste products’ of cutting the limestone. Leftover stone chips were sent to paper mills, where stone was needed as part of the sulphite pulp process for making paper. Beginning to supply the Ontario Paper Company with stone in 1913, meant not only long, hard, work, but also more profit for the company. Before mechanization, most of the loading and unloading of the stone was done by hand, taking 19 man-hours to load an 18 yard railway car. Mechanization followed in 1947 when the plant became fully mechanized making the work easier and increasing production rates. In 1957 the company moved from its original location and opened the St. Catharines Crushed Stone Plant.

Systematic stratigraphic study of cenozoic sediments of Kerala with Special reference to warkalli and quilon formations

Quaternary stratigraphy of the Kerala coast and the genetic aspects of the sediments are discussed. The age of limeshells, and peaty sediments determined by radio carbon dating have been used for reconstruction of sea level changes. Evolution of red sands occurring in some parts of the coastal tract of Kerala is also discussed, based on textural parameters and quartz grain morphology.

Classification of recycled sands and their applications as fine aggregates for concrete and bituminous mixtures

As a result of the drive towards waste-poor world and reserving the non-renewable materials, recycling the construction and demolition materials become very essential. Now reuse of the recycled concrete aggregate more than 4 mm in producing new concrete is allowed but with natural sand a fine aggregate while. While the sand portion that represent about 30\% to 60\% of the crushed demolition materials is disposed off. To perform this research, recycled concrete sand was produced in the laboratory while nine recycled sands produced from construction and demolitions materials and two sands from natural crushed limestone were delivered from three plants. Ten concrete mix designs representing the concrete exposition classes XC1, XC2, XF3 and XF4 according to European standard EN 206 were produced with partial and full replacement of natural sand by the different recycled sands. Bituminous mixtures achieving the requirements of base courses according to Germany standards and both base and binder courses according to Egyptian standards were produced with the recycled sands as a substitution to the natural sands. The mechanical properties and durability of concrete produced with the different recycled sands were investigated and analyzed. Also the volumetric analysis and Marshall test were performed hot bituminous mixtures produced with the recycled sands. According to the effect of replacement the natural sand by the different recycled sands on the concrete compressive strength and durability, the recycled sands were classified into three groups. The maximum allowable recycled sand that can be used in the different concrete exposition class was determined for each group. For the asphalt concrete mixes all the investigated recycled sands can be used in mixes for base and binder courses up to 21\% of the total aggregate mass.