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At least 523 records · Page 29

Mineralogical and chemical assessment of concrete damaged by the oxidation of sulfide-bearing aggregates: Importance of thaumasite formation on reaction mechanisms

Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivieres area (Quebec, Canada), characterized by rapid deterioration within 3 to 5 years after construction. A petrographic examination of concrete core samples was carried out using a combination of tools including: stereomicroscopic evaluation, polarized light microscopy, scanning electron microscopy, X-ray diffraction and electron microprobe analysis. The aggregate used to produce concrete was an intrusive igneous rock with different metamorphism degrees and various proportions of sulfide minerals. In the rock, sulfide minerals were often surrounded by a thin layer of carbonate minerals (siderite). Secondary reaction products observed in the damaged concrete include 'rust' mineral forms (e.g. ferric oxyhydroxides such as goethite, limonite (FeO (OH) nH{sub 2}O) and ferrihydrite), gypsum, ettringite and thaumasite. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste/aggregate and provokes the formation of sulfate minerals. Understanding both mechanisms, oxidation and internal sulfate attack, is important to be able to duplicate the damaging reaction in laboratory conditions, thus allowing the development of a performance test for evaluating the potential for deleterious expansion in concrete associated with sulfide-bearing aggregates.

36 MATERIALS SCIENCE↗

Alite-ye'elimite cement: Synthesis and mineralogical analysis

Alite-ye'elimite cement is an alternative cement that combines desirable characteristics of calcium sulfoaluminate cements and Portland cement in that it shows improved strength development at early age while retaining high portlandite contents. The key problem in the clinkering process is to produce the alite-ye'elimite phase assemblage so that both phases can co-exist. In this study, a new synthesis method is proposed to achieve the coexistence of alite and ye'elimite consisting of a secondary heat treatment step at 1250 °C after regular Portland clinker firing at 1450 °C. Quantitative X-ray powder diffraction and electron microscopy were used to analyze the phase composition of clinker before and after the secondary heat treatment. The results show that ye'elimite develops during secondary heat treatment of calcium sulphate enriched clinker by reaction of C{sub 3}A and sulphate phases. Additional ferrite is formed as result of rejection of Fe originally in solid solution with C{sub 3}A during ye'elimite formation.

36 MATERIALS SCIENCE↗

Submicron-scale mineralogy of lithotypes and the implications for trace element associations: Blue Gem coal, Knox County, Kentucky

Transmission electron microscopy accompanied by energy-dispersive spectroscopy and selected area electron diffraction of density-gradient separates from two lithotypes of the low-ash, low-sulfur Blue Gem coal, eastern Kentucky, revealed an array of previously unrecognized (in this coal, and arguable in most others) sub-micron minerals, some <10 nm in size. The first sample representing the 1.22–1.24 specific gravity fraction of the middle bench contains a mineral identified as a La-, Ce-, Nd-bearing monazite; other minerals with CrFe, CuFeS, FeZn-S, and Pb; and areas, probably comprising agglomerates of several grains, if not several minerals, with concentrations of Mg, Ca, Ti, Fe, Zn, Zr, and Mo. The second sample representing the 1.30–1.31 specific gravity fraction of the basal lithotype has aggregates of particles enriched in Mg, Ca, Ti, and Fe. Individual grains not specifically quantified include CrNiMnCuFeS, AgS, and CuS. Detailed investigation of one area (most of the variation within a <4 μm 2 region) demonstrates the presence of greenockite (CdS); minute phases containing NiCoGe and AgCdBi, the latter with a more evident S association than the former; metallic Bi; nisnite (Ni 3 Sn); silver cadmium; manganosite (MnO); and siderite. Some minerals, such as the monazite, are most likely of detrital or tuffaceous origin. Many of the other assemblages could be of hydrothermal origin, a hypothesis supported by known regional geochemical and coal rank trends, but not previously demonstrated in mineral assemblages at the 10's of nm scale in this region.

01 COAL, LIGNITE, AND PEAT↗

Safe management of actinides in the nuclear fuel cycle: Role of mineralogy

During the past 60 years, more than 1800 metric tonnes of Pu, and substantial quantities of the “minor” actinides, such as Np, Am and Cm, have been generated in nuclear reactors. Some of these transuranium elements can be a source of energy in fission reactions (e.g., 239Pu), a source of fissile material for nuclear weapons (e.g., 239Pu and 237Np), and of environmental concern because of their long-half lives and radiotoxicity (e.g., 239Pu and 237Np). There are two basic strategies for the disposition of these heavy elements: (1) to “burn” or transmute the actinides using nuclear reactors or accelerators; (2) to “sequester” the actinides in chemically durable, radiation-resistant materials that are suitable for geologic disposal. There has been substantial interest in the use of actinide-bearing minerals, especially isometric pyrochlore, A2B2O7 (A = rare earths; B = Ti, Zr, Sn, Hf), for the immobilization of actinides, particularly plutonium, both as inert matrix fuels and nuclear waste forms. Systematic studies of rare-earth pyrochlores have led to the discovery that certain compositions (B = Zr, Hf) are stable to very high doses of alpha-decay event damage. Recent developments in our understanding of the properties of heavy element solids have opened up new possibilities for the design of advanced nuclear fuels and waste forms.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mineralogical transformations in polymetallic nodules and the change of Ni, Cu and Co crystal-chemistry upon burial in sediments

Polymetallic nodules from the Clarion and Clipperton Zone of the equatorial Pacific Ocean were studied using X-ray diffraction, X-ray absorption, Fourier-transformed infrared spectroscopy and transmission electron microscopy. Here, this study includes nodules found at the sediment surface as well as subsurface (14–16 cm sediment depth) and deeply buried (530–985 cm sediment depth) nodules. The surface and subsurface nodules are currently under oxic conditions whereas the deeply buried nodules are under suboxic conditions. Surface nodules consist mainly of turbostratic phyllomanganates (7 Å and 10 Å vernadite and Fe-vernadite); todorokite is a minor phase, if present at all. In contrast, subsurface and especially deeply buried nodules predominantly consist of todorokite, which increases in abundance with depth in the sediment. Thus, upon burial of nodules within the shallow sediment, phyllomanganates transform to todorokite, probably through the combined action of time and change in the ambient chemical conditions. Nodules from deeper sediment depth (>500 cm) consist primarily of todorokite and additionally show signs of dissolution. The transformation of phyllomanganates to todorokite and their further dissolution upon nodule burial under suboxic conditions induces modifications in the crystal-chemistry of Ni, Co, and Cu. In surface nodules, Ni and Co are incorporated in the octahedral sheets of phyllomanganates, whereas Cu mainly is located at the edges of those phyllomanganate sheets. In buried nodules Cu and to a lesser extent Ni are incorporated in todorokite by forming outer-sphere complexes within the tunnels. However, Ni is predominantly incorporated within the octahedra of the newly formed todorokite structure. Co is also enriched in the octahedra of todorokite as a result of dissolution of hydrogenetic vernadite and re-incorporation in the more stable Mn-phase formed during the diagenetic transformation. Co enrichment under suboxic conditions after burial within the sediments is noteworthy since Co in surface nodules is characteristic for oxic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon sequestration into lime-stabilized soils: Engineering and mineralogical characterization

Stabilizing weak clayey soils with lime is an effective method for improving the mechanical properties of soil. However, lime production is an energy-intensive process producing significant CO 2 emissions in lime-stabilized soils, which can be counteracted through accelerated carbonation that enhances its engineering performance. The present study evaluates accelerated carbonation of lime-treated soils by adding gaseous (CO 2 -rich gas), liquid (water-CO 2 mixture), and solid (sodium bicarbonate) CO 2 sources. Results indicated that samples carbonated with gaseous CO 2 exhibited 100% lime carbonation, while samples treated with solid and aqueous sources of CO 2 had a mean lime carbonation of 60% and 40%, respectively. Further, all lime-treated-carbonated samples exhibited a mean 50% increase in unconfined compressive strength compared to the untreated samples after a 7-day curing period. Durability evaluation through cyclic wetting and drying indicated that the carbonated samples had higher durability than the untreated samples. X-ray computed tomography showed that adding solid and liquid sources of CO 2 facilitated the flocculation of montmorillonite, reducing the porosity. However, a higher dosage of solid CO 2 induced clay dispersion, increasing the porosity. X-ray diffraction and thermogravimetric analysis verified CO 2 sequestration through the formation of calcite, a thermodynamically stable polymorph of calcium carbonate.

58 GEOSCIENCES↗

Mineralogy and reactive fluid chemistry evolution of hydraulically fractured Caney shale of Southern Oklahoma

Here, this study investigates geochemical rock-fluid interactions as a potential cause of rapid loss of permeability and productivity in hydraulically fractured shale reservoirs. It also interrogates the effects of these reactions in transforming depleted shale reservoirs into impermeable carbon storage units. The study employs batch reactor experiments where rock-powder samples are reacted with field fracturing fluid under reservoir temperature (95°C).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Fe(III) (hydr)oxide mineralogy on the development of microbial communities originating from soil, surface water, groundwater, and aerosols

Microbial Fe(III) reduction is a key component of the iron cycle in natural environments. However, the susceptibility of Fe(III) (hydr)oxides to microbial reduction varies depending on the mineral's crystallinity, and the type of Fe(III) (hydr)oxide in turn will affect the composition of the microbial community. Here, we created microcosm reactors with microbial communities from four different sources (soil, surface water, groundwater, and aerosols), three Fe(III) (hydr)oxides (lepidocrocite, goethite, and hematite) as electron acceptors, and acetate as an electron donor to investigate the shaping effect of Fe(III) mineral type on the development of microbial communities. During a 10-month incubation, changes in microbial community composition, Fe(III) reduction, and acetate utilization were monitored. Overall, there was greater reduction of lepidocrocite than of goethite and hematite, and the development of microbial communities originating from the same source diverged when supplied with different Fe(III) (hydr)oxides. Furthermore, each Fe(III) mineral was associated with unique taxa that emerged from different sources. This study illustrates the taxonomic diversity of Fe(III)-reducing microbes from a broad range of natural environments.

58 GEOSCIENCES↗

Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO{sub 2} pressure

Highlights: > Accelerated carbonation studied to improve environmental properties of steel slag. > Carbonation found to occur predominantly at surface of the steel slag grains. > Combined geochemical modelling and mineral analysis revealed controlling processes. > Enhanced V-leaching with di-Ca silicate (C2S) dissolution identified as major source. > Identified mineral transformations provide guidance for further quality improvement. - Abstract: Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this study is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO{sub 2} pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 {sup o}C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO{sub 2} and the resulting pH reduction occurred within 24 h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted. The pH of the K3 slag (originally pH {+-} 12.5) was reduced by about 1.5 units, while the K1 slag showed a smaller decrease in pH from about 11.7 to 11.1. However, the pH reduction after carbonation of the K3 slag was observed to lead to an increased V-leaching. Vanadium leaching from the K1 slag resulted in levels above the limit values of the Dutch Soil Quality Decree, for both the untreated and carbonated slag. V-leaching from the carbonated K3 slag remained below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evolution of phosphorus complexation and mineralogy during (hydro)thermal treatments of activated and anaerobically digested sludge: Insights from sequential extraction and P K-edge XANES

(Hydro)thermal treatments of sewage sludge is a promising option that can simultaneously target safe waste disposal, energy recovery, and nutrient recovery/recycling. The speciation of phosphorus (P) in sludge is of great relevance to P reclamation/recycling and soil application of sludge-derived products, thus it is critical to understand the effecHere, this study systematically characterized P speciation (i.e. complexation and mineral forms) in chars derived from pyrolysis and hydrothermal carbonization (HTC) of municipal sewage sludges. Combined sequential extraction and P K-edge X-ray absorption near edge structure (XANES) spectroscopy analysis revealed the dependence of P transformation on treatment conditions and metal composition in the feedstocks. Pyrolysis of sludges decreased the relative abundance of phytic acid while increased the abundance of Al-associated P. HTC thoroughly homogenized and exposed P for interaction with various metals/minerals, with the final P speciation closely related to the composition/speciation of metals and their affinities to P. Results from this study revealed the mechanisms of P transformation during (hydro)thermal treatments of sewage sludges, and might be applicable to other biosolids. Finally, it also provided fundamental knowledge basis for the design and selection of waste management strategies for better P (re)cycling and reclamation.

54 ENVIRONMENTAL SCIENCES↗