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The construction industry is estimated to generate around 600 million tons of concrete and demolition waste annually in the US. In comparison, Waste-To-Energy (WTE) plants generate about 6.6 million tons of ash from the combustion of municipal solid waste.1–4 Research has been ongoing for decades to upcycle WTE-ash and C&D waste.
Risks associated with carbonation are a key limitation to greater replacement levels of ordinary portland cement (OPC) by supplementary cementitious materials (SCMs). The addition of pozzolanic SCMs in OPC alters the hydrate assemblage by forming phases like calcium-(alumina)-silicate-hydrate (C-(A)-S-H). The objective of the present study was to elucidate how such changes in hydrate assemblage influence the chemical mechanisms of carbonation in a realistic OPC system. Here, in this paper, we show that synthetic zeolite Y (faujasite) is a highly reactive pozzolan in OPC that reduces the calcium content of hydration products via prompt consumption of calcium hydroxide from the evolving phase assemblage prior to CO 2 exposure. Suppression of portlandite at moderate to high zeolite Y content led to a more damaging mechanism of carbonation by disrupting the formation of a passivating carbonate layer. Without this layer, carbonation depth and CO 2 uptake are increased. Binders containing 12–18% zeolite Y by volume consumed all the calcium hydroxide from OPC during hydration and reduced the Ca/(Si+Al) ratio of the amorphous products to near 0.67. In these cases, higher carbonation depths were observed after exposure to ambient air with decalcification of C-(A)-S-H as the main source of CO 2 buffering. Binders with either 0% or 4% zeolite Y contained calcium hydroxide in the hydrated microstructure, had higher Ca/(Si+Al) ratios, and formed a calcite-rich passivation layer that halted deep carbonation. Although the carbonated layer in the samples with 12% and 18% zeolite Y contained 70% and 76% less calcite than the OPC respectively, their higher carbonation depths resulted in total CO 2 uptakes that were 12x greater than the OPC sample. Passivation layer formation in samples with calcium hydroxide explains this finding and was further supported by thermodynamic modeling. High Si/Al zeolite additives to OPC should be balanced with the calcium content for optimal carbonation resistance.
Calcium magnesium aluminum silicate (CMAS) is one of the leading concerns for the gas turbine industry. The effects of CMAS viscosity and the coating microstructure on CMAS infiltration depth were explored by conducting a time dependent interaction study. Three CMAS compositions were used from literature, and their viscosities predicted through FactSage viscosity module were drastically different. The interaction was carried out on three different TBCs synthesized using the solution precursor plasma spray process (SPPS): two of the TBCs were made of yttrium aluminum garnet (YAG) having different microstructures that promote different modes of CMAS infiltration, and one TBC was made of gadolinium zirconate (GZO). All samples had stress relieving vertical cracks and different intensities of horizontally banded porosity, (inter pass boundaries IPBs). A concentration of 100 mg/cm 2 of CMAS was applied on the TBCs which were then subjected to a 5-minute interaction at 1300 °C. Samples were analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDXS), and transmission electron microscopy (TEM). Low viscosity CMAS readily penetrated the TBCs while more viscous CMAS showed less penetration. The depth of CMAS infiltration depended on the coating microstructure. In the YAG with IPBs, the CMAS spread horizontally in the IPBs before infiltrating deeper, resulting in reduced infiltration depth compared to other samples in spite of having wider vertical cracks. TEM and EDXS analysis were performed to investigate the phases present in the CMAS-TBC interaction region in YAG. Two regions were chosen, the top TBC surface in direct contact with the sea of CMAS, and the region at the CMAS penetration ended within the coating. Finally, the results showed that no secondary phases like apatite were observed in YAG, thus it can be concluded that the arrest of CMAS happened solely because of CMAS viscosity and the short infiltration time.
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Calcium–magnesium–alumino-silicate (CMAS) particulates enter the aero-engine in a sandy environment, melt and infiltrate into 7 wt% yttria-stabilized zirconia (7YSZ) thermal barrier coatings (TBCs), reducing their lifetime. This leads to chemical degradation in 7YSZ accompanied by tetragonal to monoclinic phase transformation upon cooling. In this work, electron-beam physical vapor deposition coatings were infiltrated with a synthetic CMAS. Here, synchrotron X-ray diffraction measurements show that CMAS infiltration at 1250 °C has about 43% higher monoclinic phase volume fraction (PVF) at the coating surface compared to 1225 °C and remains consistently higher throughout the coating depth. Additionally, the increase in annealing time from 1 to 10 h results in a 31% higher monoclinic phase at the surface. Scanning electron microscopy revealed the presence of globular monoclinic phases corresponding spatially with the above findings. These results resolve the impact of time and temperature on CMAS infiltration kinetics which is important for mitigation.
Silicic acid can change into various species such as deposit, colloidal, and soluble form under certain conditions: for example, gradual pH changes around geological disposal repositories. In particular, silicic acid deposits narrow groundwater flow paths, thereby restricting the flow of groundwater. Such effects may contribute to a delay in radionuclide migration. Previous studies have reported that silicic acid supersaturated in sodium and calcium ions can narrow the flow paths. This study examined the effect of magnesium (Mg) and aluminum (Al) ions on the deposition of supersaturated silicic acid on the solid phase. The deposition behavior of supersaturated silicic acid on the solid phase was investigated in a batch system while changing the initial supersaturation concentration, the coexisting ion concentration, and the amount of added solid phase. In the presence of Mg ions, silicic acid precipitation increased with increasing Mg ion concentration due to the influence of the electrolyte, and crosslinking reactions. The coexistence of Al ions significantly suppressed silicic acid deposition due to the formation of a covering on the solid surface during Al ion hydrolysis under conditions of high Al concentration (1.4 mM). On the basis of these experimental results, the apparent deposition rate constant of silicic acid was estimated to be in the range from 10{sup -11} to 10{sup -10} m/s. The Damkoehler number (the dimensionless number expressed by the ratio of the characteristic time of mass transfer and the chemical reaction constant) was sufficient to cause the clogging of the host rock by deposition. This suggests that supersaturated silicic acid deposition, regardless of the presence of Mg ions (and Al ions), contributes to improving barrier performance against radionuclide migration in the host rock. (authors)
Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)
Samples of asteroid (101955) Bennu delivered by the OSIRIS-REx mission offer the opportunity to study pristine planetary materials unchanged by exposure to the terrestrial environment. Here we use a combination of X-ray diffraction and various electron microscopy techniques to explore the detailed mineralogy of Bennu samples and determine the alteration history of the planetesimal protolith from which they originated. The samples consist largely of hydrated sheet-silicate minerals, namely nanoscale serpentine and saponite of varied grain size, which are decorated with micro- to nanoscale Fe-sulfides, magnetite and carbonates. We observe sheet silicates parallel and normal to sulfide surfaces and as inclusions in sulfides; sulfur-rich veins transecting the sheet-silicate matrix; zoned carbonates and phosphates and sulfide and magnetite grains exhibiting embayment. The mineralogical evidence indicates alteration of accreted minerals by a fluid that evolved with time, leading to etching, dissolution and reprecipitation. Sulfide compositions indicate alteration at ~25 °C, similar to conditions inferred for asteroid (162173) Ryugu and Ivuna-type (CI) chondrite meteorites. The fluid probably evolved from neutral to alkaline, culminating with the precipitation of highly soluble salts. We conclude that Bennu’s protolith comprised mainly nanometre to micrometre silicates, with fewer chondrules and calcium–aluminium-rich inclusions than those of most chondrite groups.
Resistance to carbonation is one important attribute that low-CO{sub 2} cement alternatives must possess, and is particularly crucial for cement alternatives subjected to aggressive CO{sub 2} concentrations such as those used in construction of oil wells and wells for below ground carbon sequestration. Here, a parametric study of alkali-activated slag (AAS) carbonation in aggressive environments has been conducted to examine (i) calcium carbonate polymorphism using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy, and (ii) the extent of calcium carbonate formation and CO{sub 2} adsorption using thermogravimetric analysis (TGA). A range of AASs have been studied by varying the magnesium content of the slag, the activator type (sodium hydroxide and sodium silicate), the activator concentration, and the curing time prior to carbonation. It was uncovered that both (i) magnesium from the slag and (ii) silica from the activating solution are needed to reduce the propensity for the sodium-containing calcium-alumino-silicate-hydrate gel to undergo decalcification.
Carbon mineralization to solid carbonates is one of the reaction pathways that can not only utilize captured CO 2 but also potentially store it in the long term. In this study, the dissolution and carbonation behaviors of alkaline solid wastes (i.e., waste concrete) was investigated. Concrete is one of the main contributors to a large carbon emission in the built environment. Thus, the upcycling of waste concrete via CO 2 utilization has multifaceted environmental benefits including CO 2 emission reduction, waste management and reduced mining. Unlike natural silicate minerals such as olivine and serpentine, alkaline solid wastes including waste concrete are highly reactive, and thus, their dissolution and carbonation behaviors vary significantly. Here, both conventional acid (e.g., hydrochloric acid) and less studied carbonic acid (i.e., CO 2 saturated water) solvent systems were explored to extract Ca from concrete. Non-stoichiometric dissolution behaviors between Ca and Si were confirmed under far-from-equilibrium conditions (0.1 wt% slurry density), and the re-precipitation of the extracted Si was observed at near-equilibrium conditions (5 wt% slurry density), when the Ca extraction was performed at a controlled pH of 3. These experiments, with a wide range of slurry densities, provided valuable insight into Si re-precipitation phenomena and its effect on the mass transfer limitation during concrete dissolution. Next, the use of the partial pressure of CO 2 for the pH swing carbon mineralization process was investigated for concrete, and the results were compared to those of Mg-bearing silicate minerals. In the P CO 2 swing process, the extraction of Ca was significantly limited by the precipitation of the carbonate phase (i.e., calcite), since CO 2 bubbling could not provide a low enough pH condition for concrete–water–CO 2 systems. Furthermore, this study showed that the two-step carbon mineralization via P CO 2 swing, that has been developed for Mg-bearing silicate minerals, may not be viable for highly reactive Ca-bearing silicate materials (e.g., concrete). The precipitated calcium carbonate (PCC) derived from waste concrete via a pH swing process showed very promising results with a high CO 2 utilization potential as an upcycled construction material.
The impact of calcium hydroxide as an additive in sodium hydroxide- and silicate-activated metakaolin pastes is presented with a primary aim to ascertain the specific effects of calcium on the reaction kinetics and phase formation. FTIR and XRD are employed to understand the interaction of calcium hydroxide (10 wt% replacement of metakaolin) in 1, 5 and 10 M NaOH-activated pastes (and equivalent molarity Na{sub 2}SiO{sub 3}-activated pastes), with a focus on its impact on the nanoscale properties of the sodium-alumino-silicate-hydrate (N-A-S-(H)) gel. In situ FTIR and ICC are used to assess the impact of calcium hydroxide on the reaction kinetics, including the rate of metakaolin dissolution and associated rate of N-A-S-(H) gel growth. It is found that calcium hydroxide is effective at accelerating the reaction kinetics of 5 M Na{sub 2}SiO{sub 3}-activated metakaolin due to the formation of an initial calcium-rich gel that promotes additional metakaolin dissolution and enhances N-A-S-(H) gel formation.
Efflorescence can be harmful to material performance as a consequence of microstructural changes due to leaching and carbonation of alkalis. This article identifies mechanisms of efflorescence in metakaolin-based geopolymers, and approaches to reduce free/mobile alkali cations and pore network connectivity, and hence reduce efflorescence. Mechanical, mass transport and microstructural properties are assessed in metakaolin-based geopolymer cements produced using different alkali concentrations in the alkali activator and substitution/addition of blast furnace slag, silica fume, calcium aluminate cement, silicone oil and a dispersive admixture. The most effective strategy to reduce efflorescence results from increasing Si/Al in the geopolymer gel by addition of soluble silicate, silica fume or silicone oil. Addition of calcium aluminate cement or a dispersive admixture also reduce efflorescence, but are less effective. These results confirm that efflorescence may be reduced by controlling the amount of soluble silicates and reducing free alkali cations in geopolymers, providing enhanced performance and durability.
Abstract Calcareous sponges are an often overlooked element of sponge communities. In contrast to most other sponges, calcareous sponges produce calcium carbonate spicules, as opposed to the siliceous spicules of most sponges. Here, we investigated the bacterial communities of 17 sponge species, including type and paratype specimens of recently described calcareous species, sampled off the remote island of Rodrigues, in the Indian Ocean. The main axis of variation in a PCO analysis of all samples separated noncalcareous sponge species, including Axinyssa aplysinoides, Cinachyrella aff. australiensis, Petrosia seychellensis, Ircinia aff. variabilis, Spongia ceylonensis, Plakinastrella aff. clipptertonensis, Agelas aff. ceylonica, Agelas aff. mauritiana, and Hyrtios erectus from calcareous sponges, the noncalcareous Biemna tubulata, sediment, and seawater. Overall, the bacterial communities of calcareous sponges revealed unique prokaryotic profiles with low abundances of several bacterial phyla, and relatively high abundances of other taxa, for example, the phyla Fibrobacterota, Proteobacteria, and the SAR324 clade, the class Alphaproteobacteria, and orders Cytophagales and Cyanobacteriales, although there was considerable variation among species. Calcareous sponges also had a high dominance of unknown bacterial operational taxonomic units (OTUs). Considering the unique nature of these communities, further studies are needed to better understand the environmental and ecological drivers of calcareous sponge-associated bacterial communities and their relevance as potential sources of novel microbes of biotechnological interest.
Alkali-activated slag (AAS) is a promising low-CO 2 alternative cement consisting of several disordered phases of similar composition. Although their local atomic arrangements are known to influence macroscopic behavior, determination of structural changes in response to external stimuli remains a challenge. Here, X-ray diffraction-computed tomography (XRD-CT), pair distribution function-CT (PDF-CT), and nanoprobe X-ray fluorescence (nano-XRF) have been used to uncover how an increase of magnesium in AAS affects the atomic structure and spatial arrangement of phases after aggressive carbonation (100% dry CO 2 ), conditions experienced in applications such as oil and gas wells and geological storage of CO 2 . From PDF-CT it is found that a higher magnesium content decreases the average nanoscale crystallite size of disordered calcium carbonate. At the same time, higher magnesium content is correlated with a less decalcified C-(N)-A-S-H gel, as determined via analysis of Ca-Si atom-atom correlations from PDF-CT and Ca/Si ratios from nano-XRF. Finally, nano-XRF reveals that the disordered (i.e., amorphous) calcium carbonate is stabilized by the presence of silicates.
The meteorite Lieksa was found in 2017 in Löpönvaara, Finland, and later donated to the Finnish Museum of Natural History. Here, we report siderophile element concentrations, genetic isotopic data, and a metal–silicate segregation age for the meteorite. The ~280 g Lieksa is ~80% metal and ~20% silicate and oxide inclusions by volume, with the inclusions consisting primarily of Fe-rich olivine. Due to Lieksa's silicate content, coupled with a texture characterized by metal enclosing the silicates, it has been classified as a pallasite. Lieksa's olivine and bulk chemical characteristics are distinct from those of the known pallasite and iron meteorite groups, consistent with its classification as ungrouped. The meteorite exhibits a flat, chondrite-normalized highly siderophile element pattern, consistent with an origin as an early crystallization product from a metallic melt with chondritic relative abundances. Molybdenum, Ru, and 183 W isotopic data indicate that Lieksa formed in the non-carbonaceous (NC) domain of the solar nebula. Radiogenic 182 W abundances for Lieksa yield a model metal–silicate segregation age of 1.5 ± 0.8 Myr after calcium-aluminum-rich inclusion formation, which is within the range established for other NC-type pallasite and iron meteorite parent bodies.
Highlights: • The synthesis of high-purity ternesite based on a single-stage sintering process was firstly studied. • The formation mechanism and crystallization behaviour of ternesite during sintering were investigated. • The structure perfection and symmetry of ternesite crystals were increased with its growth. • The growth and structural development of ternesite crystals during sintering resulted in a higher thermal stability of itself. Ternesite was prepared via a single-stage solid-state reaction from stoichiometric quantities of the CaCO{sub 3}, SiO{sub 2} and CaSO{sub 4}·2H{sub 2}O precursors. In this paper, the formation, structure, and thermal stability evolution of ternesite during sintering were investigated ex situ after quenching. The optimal sintering temperature for the formation of high-purity ternesite was approximately 1200 °C for 12 h, of which the purity level can reach as high as 96.3%. The results from scanning electron microscopy analysis suggest that the formation of ternesite benefited from the preformation of the intermediate silicate phase. Increasing the sintering temperature from 1100 °C to approximately 1250 °C was favourable for the growth of ternesite crystals, and a prolonged duration can also promote this behaviour. The structural perfection and symmetry of ternesite crystals increased with its growth, which was demonstrated by a multimethod approach. By means of thermal analysis, the growth and structural development of ternesite crystals during sintering eventually resulted in a higher thermal stability.
Alkali-silica reaction (ASR) is a significant cause of the degradation of concrete structures. ASR results from the dissolution of reactive silicate aggregates and the subsequent formation of damaging, expansive ASR gels. Despite the prevalence of ASR, so far only lithium-based chemical admixtures have been shown to be successful in mitigating its deleterious effects. Herein, dissolved calcium nitrate (Ca(NO 3 ) 2 : CN) is demonstrated to reduce ASR-induced expansion caused by the use of sodium borosilicate (NBS) glass as a model reactive aggregate. The significance of reductions of NBS-glass dissolution and mortar-bar expansion rates is discussed, with special focus on highlighting the mechanism by which calcium nitrate mitigates ASR, i.e., by the inhibition of aggregate dissolution. This study reveals a new and cost-effective pathway to suppress aggregate dissolution and ASR in concrete based on the dosage of soluble alkaline-earth additives.