Industrial by-products-derived binders for in-situ remediation of high Pb content pyrite ash: Synergistic use of ground granulated blast furnace slag and steel slag to achieve efficient Pb retention and CO2 mitigation.

Ordinary Portland cement (OPC) is a cost-effective and conventional binder that is widely adopted in brownfield site remediation and redevelopment. However, the substantial carbon dioxide emission during OPC production and the concerns about its undesirable retention capacity for potentially toxic elements strain this strategy. To tackle this objective, we herein tailored four alternative binders (calcium aluminate cement, OPC-activated ground-granulated blast-furnace slag (GGBFS), white-steel-slag activated GGBFS, and alkaline-activated GGBFS) for facilitating immobilization of high Pb content pyrite ash, with the perspectives of enhancing Pb retention and mitigating anthropogenic carbon dioxide emissions. The characterizations revealed that the incorporation of white steel slag efficiently benefits the activity of GGBFS, herein facilitating the hydration products (mainly ettringite and calcium silicate hydrates) precipitation and Pb immobilization. Further, we quantified the cradle-to-gate carbon footprint and cost analysis attributed to each binder-Pb contaminants system, finding that the application of these alternative binders could be pivotal in the envisaged carbon-neutral world if the growth of the OPC-free roadmap continues. The findings suggest that the synergistic use of recycled white steel slag and GGBFS can be proposed as a profitable and sustainable OPC-free candidate to facilitate the management of lead-contaminated brownfield sites. The overall results underscore the potential immobilization mechanisms of Pb in multiple OPC-free/substitution binder systems and highlight the urgent need to bridge the zero-emission insights to sustainable in-situ solidification/stabilization technologies.

Mechanistic insights into Pb and sulfates retention in ordinary Portland cement and aluminous cement: Assessing the contributions from binders and solid waste.

Identifying immobilization mechanisms of potentially toxic elements (PTEs) is of paramount importance in the field application of solidification/stabilization. Traditionally, demanding and extensive experiments are required to better access the underlying retention mechanisms, which are usually challenging to quantify and clarify precisely. Herein, we present a geochemical model with parametric fitting techniques to reveal the solidification/stabilization of Pb-rich pyrite ash through conventional (ordinary Portland cement) and alternative (calcium aluminate cement) binders. We found that ettringite and calcium silicate hydrates exhibit strong affinities for Pb at alkaline conditions. When the hydration products are unable to stabilize all the soluble Pb in the system, part of the soluble Pb may be immobilized as Pb(OH)2. At acidic and neutral conditions, hematite from pyrite ash and newly-formed ferrihydrite are the main controlling factors of Pb, coupled with anglesite and cerussite precipitation. Thus, this work provides a much-needed complement to this widely-applied solid waste remediation technique for the development of more sustainable mixture formulations.

Detecting Early-Stage Cohesion Due to Calcium Silicate Hydration with Rheology and Surface Force Apparatus.

Extremely robust cohesion triggered by calcium silicate hydrate (C-S-H) precipitation during cement hardening makes concrete one of the most commonly used man-made materials. Here, in this proof-of-concept study, we seek an additional nanoscale understanding of early-stage cohesive forces acting between hydrating model tricalcium silicate (C3S) surfaces by combining rheological and surface force measurements. We first used time-resolved small oscillatory rheology measurements (SAOSs) to characterize the early-stage evolution of the cohesive properties of a C3S paste and a C-S-H gel. SAOS revealed the reactive and viscoelastic nature of C3S pastes, in contrast with the nonreactive but still viscoelastic nature of the C-S-H gel, which proves a temporal variation in the cohesion during microstructural physicochemical rearrangements in the C3S paste. We further prepared thin films of C3S by plasma laser deposition (PLD) and demonstrated that these films are suitable for force measurements in the surface force apparatus (SFA). We measured surface forces acting between two thin C3S films exposed to water and subsequent in situ calcium silicate hydrate precipitation. With the SFA and SFA-coupled interferometric measurements, we resolved that C3S surface reprecipitation in water was associated with both increasing film thickness and progressively stronger adhesion (pull-off force). The lasting adhesion developing between the growing surfaces depended on the applied load, pull-off rate, and time in contact. These properties indicated the viscoelastic character of the soft, gel-like reprecipitated layer, pointing to the formation of C-S-H. Our findings confirm the strong cohesive properties of hydrated calcium silicate surfaces that, based on our preliminary SFA measurements, are attributed to sharp changes in the surface microstructure. In contact with water, the brittle and rough C3S surfaces with little contact area weather into soft, gel-like C-S-H nanoparticles with a much larger surface area available for forming direct contacts between interacting surfaces.

Capture and Release Mechanism of Ni and La Ions via Solid/Liquid Process: Use of Polymer-Modified Clay and Activated Carbons.

This study is a starting point for the development of an efficient method for rare earths (REs) and transition metals (TMs) recovery from waste electrical and electronic equipment (WEEE) via a hydrometallurgical process. The capture and release capability of mineral clays (STx) and activated carbons (AC), pristine and modified (STx-L6 and AC-L6) with a linear penta-ethylene-hexamine (L6), towards solutions representative of the process, are assessed in the lab-scale. The solids were contacted with synthetic mono- and bi-ionic solutions containing Ni(II) and La(III) in a liquid/solid adsorption process. Contacting experiments were carried out at room temperature for 90 min by fixing a La concentration at 19 mM and varying the Ni one in the range of 19-100 mM. The four solids were able to capture Ni(II) and La(III), both in single- and bi-ionic solutions; however, the presence of the polyamine always results in a large improvement in the capture capability of the pristine sorbents. For all the four solids, capture behaviour is ascribable to an adsorption or ion-sorbent interaction process, because no formation of aquo- and hydroxy-Ni or La can be formed. The polyamine, able to capture Ni ions via coordination, allowed to differentiate ion capture behaviour, thus bypassing the direct competition between Ni and La ions for the capture sites found in the pristine solids. Release values in the 30-100% range were found upon one-step treatment with concentrated HNO3 solution. However, also, in this case, different metals recovery was found depending on both the sorbent and the ions, suggesting a possible selective recovery.

A Fresh View on Limestone Calcined Clay Cement (LC3) Pastes.

In this work, the factors controlling the fresh state properties of limestone calcined clay cement (LC3) are assessed and compared to Portland and binary cements, extending the scope of previous research by combining rheological measurements with setting time determination and the evaluation of plastic shrinkage by a novel method. Yield stress and elastic modulus are considered indicators for the structural build-up/breakdown process when stress is applied to the system. On the other hand, plastic shrinkage occurs from the mixing to the setting of fresh paste and plays an important role in governing microstructural changes due to settlement and evaporation. Evaluation of the rheological properties with time was appropriate to give an overview of the influence and behavior of different added materials. The elastic modulus of all binders (clinker, LC3, clinker-limestone, and clinker-calcined clay) was increased from mixing to 60 min of curing as follows: 5.27 × 103 to 9.50 × 105 Pa, 5.94 × 103 to 9.87 × 105 Pa, 6.89 × 103 to 5.62 × 105 Pa and 7.85 × 103 to 1.27 × 106 Pa, respectively. Moreover, during the first three hours of curing, LC3 exhibited a reduction of plastic shrinkage by more than a factor of 2 compared to clinker cement. The use of calcined clay with clinker increases the elastic modulus of the system due to the flocculation effect and increased water absorption, while a dilution effect is contributed due to deflocculation and a free-water increase in the system when a high fraction of limestone is present in the binary cement. The combination of limestone and calcined clay with clinker can induce additional chemical reactions, which control the early age properties, such as plastic shrinkage. The obtained results can contribute to optimizing the fresh state properties of ternary blends of OPC, calcined clay, and limestone through a knowledge-based approach.

Heavy-Metal Phytoremediation from Livestock Wastewater and Exploitation of Exhausted Biomass.

Sustainable agriculture is aimed at long-term crop and livestock production with a minimal impact on the environment. However, agricultural practices from animal production can contribute to global pollution due to heavy metals from the feed additives that are used to ensure the nutritional requirements and also promote animal health and optimize production. The bioavailability of essential mineral sources is limited; thus, the metals are widely found in the manure. Via the manure, metallic ions can contaminate livestock wastewater, drastically reducing its potential recycling for irrigation. Phytoremediation, which is an efficient and cost-effective cleanup technique, could be implemented to reduce the wastewater pollution from livestock production, in order to maintain the water conservation. Plants use various strategies for the absorption and translocation of heavy metals, and they have been widely used to remediate livestock wastewater. In addition, the pollutants concentrated in the plants can be exhausted and used as heat to enhance plant growth and further concentrate the metals, making recycling a possible option. The biomass of the plants can also be used for biogas production in anaerobic fermentation. Combining phytoremediation and biorefinery processes would add value to both approaches and facilitate metal recovery. This review focuses on the concept of agro-ecology, specifically the excessive use of heavy metals in animal production, the various techniques and adaptations of the heavy-metal phytoremediation from livestock wastewater, and further applications of exhausted phytoremediated biomass.

Stabilization of lead contaminated soil with traditional and alternative binders.

The application of an innovative solidification/stabilization (S/S) process was investigated for the remediation of Pb contaminated soil. The performance of Pb stabilization was evaluated by comparing the use of calcium aluminate cement (CAC) and an alkali activated metakaolin binder vs the Ordinary Portland Cement (OPC). The phase composition of the stabilized products was investigated by XRD and correlated to the internal microstructure obtained by SEM-EDX imaging. Leaching tests were performed to ascertain the effectiveness of the proposed binders in the S/S of the contaminated soil, and Pb release was evaluated for each binding system. The overall results proved that multiple mechanisms are involved in Pb retention and that key parameters regulating the stabilization performance are strongly dependent on the type of applied binder system. Pb was found to be associated to C-S-H in the case of OPC, whereas ettringite played a key role in the retention of this contaminant using the CAC binder. The use of a NaOH activated metakaolin resulted in almost total retention of Pb, despite a lack of solidification, highlighting the importance of pH in the regulation of the leaching behavior.

Simple ions control the elasticity of calcite gels via interparticle forces.

Suspensions of calcite in water are employed in many industrial fields such as paper filling, pharmaceutics or heritage conservation. Whereas organics are generally used to tune the rheological properties of the paste, we also expect simple ions to be able to control the suspension rheology via the interparticle forces. We have thus investigated the impact of calcium, sodium and hydroxide ions on the elasticity of a colloidal gel of nanocalcite. We confront our macroscopic measurements to DLVO interaction potentials, based on chemical speciation and measurements of the zeta potential. Upon addition of calcium hydroxide, we observe a minimum in shear modulus, correlated to a maximum in the DLVO energy barrier, due to two competing effects: Calcium adsorption onto calcite surface rises the zeta potential, while increasing salt concentration induces stronger electrostatic screening. We also demonstrate that the addition of sodium hydroxide completely screens the surface charge and leads to a more rigid paste. A second important result is that carbonation of the calcite suspensions by the atmospheric CO2 leads to a convergent high elasticity of the colloidal gels, whatever their initial value, also well rationalized by DLVO theory and resulting from a decrease in zeta potential.

Elasticity and yielding of a calcite paste: scaling laws in a dense colloidal suspension.

We address the mechanical characterization of a calcite paste as a model system to investigate the relation between the microstructure and macroscopic behavior of colloidal suspensions. The ultimate goal is to achieve control of the elastic and yielding properties of calcite which will prove valuable in several domains, from paper coating to paint manufacture and eventually in the comprehension and control of the mechanical properties of carbonate rocks. Rheological measurements have been performed on calcite suspensions over a wide range of particle concentrations. The calcite paste exhibits a typical colloidal gel behavior, with an elastic regime and a clear yield strain above which it enters a plastic regime. The yield strain shows a minimum when increasing the solid concentration, connected to a change in the power law scaling of the storage modulus. In the framework of the classical fractal elasticity model for colloidal suspensions proposed by Shih et al. [Phys. Rev. A, 1990, 42, 4772], we interpret this behavior as a switch with the concentration from the strong-link regime to the weak-link regime, which had never been observed so far in one well-defined system without external or chemical forcing.