The Phosphorus Transport in Groundwater from Phosphogypsum-Based Cemented Paste Backfill in a Phosphate Mine: A Numerical Study.

Stacked phosphogypsum (PG) can not only cause a waste of resources but also has a serious negative impact on the surface environment. Phosphogypsum backfilling (PGB) in the underground goaf is a useful approach to effectively address the PG environmental problems. However, the effects of this approach on the groundwater environment have not been studied. Therefore, the present study aims to assess the spatiotemporal evolution mechanism of total phosphorus (TP) in groundwater to solve the diffusion regular pattern of TP in PGB bodies, as well as to manage and mitigate the impacts of TP on the groundwater system. In this study, leaching toxicity experiments and a numerical groundwater simulation software (GMS10.4) were combined to develop a three-dimensional conceptual model for predicting the groundwater flow and contaminant transport under steady-state conditions in a phosphorus mine in Anhui. The results showed a lower TP concentration than the TP standard concentration (0.2 mg/L) at a source concentration of 0.59 mg/L. However, groundwater TP source concentrations of 1.88 and 2.46 mg/L in the study area were found to exceed the standard concentration for a certain time and areas. In addition, the transport and dispersion of TP are influenced not only by the groundwater flow field, drainage ditches, rivers, and wells but also by the adsorption and attenuation effects of the soil that occur during the transport process, affecting the dispersion distance and distribution of groundwater TP concentrations. The results of the present study can promote the development of groundwater-friendly PGB technology, providing a great significance to the construction of green mines and the promotion of ecological civilization.

Influence of CaO on Physical and Environmental Properties of Granulated Copper Slag: Melting Behavior, Grindability and Leaching Behavior.

Due to its potential pozzolanic activity, granulated copper slag (GCS) has been proven to act as a supplementary cementitious material (SCM) after thermochemical modification with CaO. This modification method reduces cement consumption and CO2 emissions; however, the additional energy consumption and environmental properties are also not negligible. This paper aims to evaluate the economics and environmental properties of thermochemically modified GCS with CaO through the melting temperature, grindability, and heavy metal leaching characteristics. The X-ray fluorescence spectroscopy (XRF) results indicated that the composition of the modified GCS shifted to the field close to that of class C fly ash (FA-C) in the CaO-SiO2-Al2O3 ternary phase diagram, demonstrating higher pozzolanic activity. The test results on melting behavior and grindability revealed that adding CaO in amounts ranging from 5 wt% to 20 wt% decreased the melting temperature while increasing the BET surface area, thus significantly improving the thermochemical modification's economics. The unconfined compressive strength (UCS) of the cement paste blended with 20 wt% CaO added to the modified GCS after curing reached 17.3, 33.6, and 42.9 MPa after curing for 7, 28, and 90 d, respectively. It even exceeded that of Portland cement paste at 28 d and 90 d curings. The leaching results of blended cement proved that the heavy metal elements showed different trends with increased CaO content in modified GCS, but none exceeded the limit values. This paper provides a valuable reference for evaluating thermochemically modified GCS's economics and environmental properties for use as SCM.

Environmental Benefit Assessment of Blended Cement with Modified Granulated Copper Slag.

This study aimed to investigate the environmental impact of modified granulated copper slag (MGCS) utilization in blended cement production at a representative cement plant in China. Sensitivity analysis was performed on the substance inputs, and the life cycle impact assessment (LCIA) model was applied. A detailed comparative analysis was conducted of the environmental impact of cement production in other studies, and ordinary Portland cement production at the same cement plant. Results showed that calcination has the largest contribution impact of all the impact categories, especially in causing global warming (93.67%), which was the most prominent impact category. The life cycle assessment (LCA) result of blended cement was sensitive to the chosen LCIA model and the depletion of limestone and energy. In this study, producing blended cement with MGCS effectively mitigated the environmental impact for all the selected impact categories. Results also show a reduction in abiotic depletion (46.50%) and a slight growth (6.52%) in human toxicity. The adoption of MGCS in blended cement would therefore generally decrease the comprehensive environmental impact of cement, which contributes to the development of sustainable building materials.

Hydration and Mechanical Properties of Blended Cement with Copper Slag Pretreated by Thermochemical Modification.

The application of granulated copper slag (GCS) to partially replace cement is limited due to its low pozzolanic activity. In this paper, reconstituted granulated copper slag (RGCS) was obtained by adding alumina oxide (Al2O3) to liquid copper slag. Blended cement pastes were formulated by a partial substitute for ordinary Portland cement (OPC) with the RGCS (30 wt%). The pozzolanic activity, mechanical development, and the microstructure were characterized. The results show that 5-10 wt% Al2O3 contributes to the increase in magnetite precipitation in RGCS. The addition of Al2O3 alleviates the inhibition of C3S by RGCS and accelerates the dissociation of RGCS active molecules, thus increasing the exothermic rate and cumulative heat release of the blended cement pastes, which are the highest in the CSA10 paste with the highest Al2O3 content (10 wt%) in RGCS. The unconfined compressive strength (UCS) values of blended cement mortar with 10 wt% Al2O3 added to RGCS reach 27.3, 47.4, and 51.3 MPa after curing for 7, 28 and 90 d, respectively, which are the highest than other blended cement mortars, and even exceed that of OPC mortar at 90 d of curing. The pozzolanic activity of RGCS is enhanced with the increase in Al2O3 addition, as evidenced by more portlandite being consumed in the CSA10 paste, forming more C-S-H (II) gel with a higher Ca/Si ratio, and a more compact microstructure with fewer pores than other pastes. This work provided a novel, feasible, and clean way to enhance the pozzolanic activity of GCS when it was used as a supplementary cementitious material.

Upconversion-nanoparticle-functionalized Janus micromotors for efficient detection of uric acid.

We report enzyme-powered upconversion-nanoparticle-functionalized Janus micromotors, which are prepared by immobilizing uricase asymmetrically onto the surface of silicon particles, to actively and rapidly detect uric acid. The asymmetric distribution of uricase on silicon particles allows the Janus micromotors to display efficient motion in urine under the propulsion of biocatalytic decomposition of uric acid and simultaneously detect uric acid based on the luminescence quenching effect of the UCNPs modified on the other side of SiO2. The efficient motion of the motors greatly enhances the interaction between UCNPs and the quenching substrate and improves the uric acid detection efficiency. Overall, such a platform using uric acid simultaneously as the detected substrate and motion fuel offers considerable promise for developing multifunctional micro/nanomotors for a variety of bioassay and biomedical applications.

Bubble-Propelled Janus Gallium/Zinc Micromotors for the Active Treatment of Bacterial Infections.

We report a bubble-propelled Janus gallium/zinc (Ga/Zn) micromotor with good biocompatibility and biodegradability for active target treatment of bacteria. The Janus Ga/Zn micromotors are fabricated by asymmetrically coating liquid metal Ga on Zn microparticles and display self-propulsion in simulated gastroenteric acid (pH 0.5) at a speed of up to 383 µm s-1 , propelled by hydrogen bubbles generated by the zinc-acid reaction. This motion of Ga/Zn micromotors is enhanced by the Ga-Zn galvanic effect. The GaIII cations produced from the degradation of Ga/Zn micromotors serve as a built-in antibiotic agent. The movement improves the diffusion of GaIII and results in a significant increase of the antibacterial efficiency against H. pylori, compared with passive Ga microparticles. Such Ga/Zn micromotors combine the self-propulsion, good biocompatibility and biodegradability, and Ga-based antibacterial properties, providing a proof of concept for the active treatment of bacterial infections.

Leukocyte Membrane-Coated Liquid Metal Nanoswimmers for Actively Targeted Delivery and Synergistic Chemophotothermal Therapy.

We report a leukocyte membrane-coated gallium nanoswimmer (LMGNS) capable of ultrasound-propelled motion, antibiofouling, and cancer cell recognition and targeting. The LMGNS consists of a needle-shaped gallium core encapsulating an anticancer drug and a natural leukocyte membrane shell. Under the propulsion of an ultrasound field, LMGNSs could autonomously move in biological media with a speed up to 108.7 µm s-1. The velocity and motion direction of the LMGNSs can be modulated by regulating the frequency and voltage of the applied ultrasound field. Owing to the leukocyte membrane coating, LMGNSs can not only avoid biofouling during the motion in blood but also possess cancer cell recognition capability. These LMGNSs could actively seek, penetrate, and internalize into the cancer cells and achieve enhanced anticancer efficiency by combined photothermal and chemical therapy. Such biofunctionalized liquid metal nanoswimmer presents a new type of multifunctional platform for biomedical applications.

Autonomous Motion of Bubble-Powered Carbonaceous Nanoflask Motors.

We report a carbonaceous nanomotor with a characteristic flask-like hollow structure that can autonomously move under the propulsion of oxygen bubbles. The carbonaceous nanoflask (CNF) motor was fabricated by encapsulating platinum nanoparticles (Pt NPs) into the hollow cavity of the CNF. The internally encapsulated Pt NPs act as catalysts to decompose hydrogen peroxide (H2O2) fuel into oxygen bubbles. The generated oxygen bubbles recoil the motion of the CNF motors. Besides, the velocity of CNF motors can be controlled by adjusting the concentration of the H2O2 solution. The motion velocity increases with the increase of H2O2 concentration, up to 109.25 µm s-1 at 10% H2O2. This study provides important implications for understanding the motion behaviors of nanomotors with an internal cavity, and the self-propelled CNF motors as smart carrier systems have potential applications in the future.

Reconfigurable Assembly of Active Liquid Metal Colloidal Cluster.

We report the reconfigurable assembly of rod-shaped eutectic gallium-indium alloy (EGaIn) liquid metal colloidal motors by mimicking the growth behavior of a dandelion. EGaIn nanorods with a diameter of 210 nm and a length of 850 nm were synthesized via an ultrasound-assisted physical dispersion method. The nanorods possess a core-shell structure with a 30 nm GaOOH shell and zero-valent liquid core. The EGaIn motors move autonomously at a speed of 41.2 µm s-1 under an acoustic field. By modulating the frequency of the applied acoustic field, the EGaIn colloidal motors self-organize into various striped and circular patterns, followed by a flower-like cluster. The dandelion-like EGaIn colloidal motor clusters move collectively and redisperse when the applied acoustic frequency is changed. Numerical simulations reveal that the flower-like clusters are created by the acoustic propulsion in combination with steric repulsion and hydrodynamics.

Janus-micromotor-based on-off luminescence sensor for active TNT detection.

An active TNT (2,4,6-trinitrotoluene) catalytic sensor based on Janus upconverting nanoparticle (UCNP)-functionalized micromotor capsules, displaying "on-off" luminescence with a low limit of detection has been developed. The Janus capsule motors were fabricated by layer-by-layer assembly of UCNP-functionalized polyelectrolyte microcapsules, followed by sputtering of a platinum layer onto one half of the capsule. By catalytic decomposition of hydrogen peroxide to oxygen bubbles, the Janus UCNP capsule motors are rapidly propelled with a speed of up to 110 µm s-1. Moreover, the Janus motors display efficient on-off luminescent detection of TNT. Owing to the unique motion of the Janus motor with bubble generation, the likelihood of collision with TNT molecules and the reaction rate between them are increased, resulting in a limit of detection as low as 2.4 ng mL-1 TNT within 1 minute. Such bubble-propelled Janus UCNP capsule motors have great potential for contaminated water analysis.

Red Blood Cell-Mimicking Micromotor for Active Photodynamic Cancer Therapy.

Photodynamic therapy (PDT) is a promising cancer therapeutic strategy, which typically kills cancer cells through converting nontoxic oxygen into reactive oxygen species using photosensitizers (PSs). However, the existing PDTs are still limited by the tumor hypoxia and poor targeted accumulation of PSs. To address these challenges, we here report an acoustically powered and magnetically navigated red blood cell-mimicking (RBCM) micromotor capable of actively transporting oxygen and PS for enhanced PDT. The RBCM micromotors consist of biconcave RBC-shaped magnetic hemoglobin cores encapsulating PSs and natural RBC membrane shells. Upon exposure to an acoustic field, they are able to move in biological media at a speed of up to 56.5 µm s-1 (28.2 body lengths s-1). The direction of these RBCM micromotors can be navigated using an external magnetic field. Moreover, RBCM micromotors can not only avoid the serum fouling during the movement toward the targeted cancer cells but also possess considerable oxygen- and PS-carrying capacity. Such fuel-free RBCM micromotors provide a new approach for efficient and rapid active delivery of oxygen and PSs in a biofriendly manner for future PDT.

Hydration and strength development in blended cement with ultrafine granulated copper slag.

This study aims at evaluating the effect of ultrafine granulated copper slag (UGCS) on hydration development of blended cement and mechanical properties of mortars. The UGCS with the median particle size of 4.78 µm and BET surface area of 1.31 m2/g was used as a cement replacement to prepare blended cements. Hydration heat emission of blended cement and mechanical performance of mortars were investigated by using isothermal calorimetry and strength tests, respectively. X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) were applied to the analysis of pozzolanic reaction and hydration products. The results illustrate that UGCS has influence on the hydration heat evolution of blended cement due to its filler effect and pozzolanic reaction. The cumulative hydration heat of blended cement is reduced by partial cement replacement with UGCS. The test mortar prepared by using blended cements with 30 wt. % UGCS shows a retardation of strength development with a low value at early ages (7 days) and a rapid growth at later ages (28 days). The 90-day compressive strength of test mortar is 45.0 MPa close to that of the control mortar (49.5 MPa). The obtained results from XRD and TGA analysis exhibit an increase in calcium hydroxide (CH) consumption and calcium silicate hydrates (C-S-H) formation in blended cement pastes with curing time. The cement replacement with UGCS induces changes in microstructure of blended cement paste and chemical composition of hydration products.

Continuously Variable Regulation of the Speed of Bubble-Propelled Janus Microcapsule Motors Based on Salt-Responsive Polyelectrolyte Brushes.

The engineering of self-propelled micro-/nanomotors (MNMs) with continuously variable speeds, akin to macroscopic automobiles equipped with a continuously variable transmission, is still a huge challenge. Herein, after grafting with salt-responsive poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMETAC) brushes, bubble-propelled Janus microcapsule motors with polyelectrolyte multilayers exhibited adjustable speeds when the type and concentration of the counterion was changed. Reversible switching between low- and high-speed states was achieved by modulating the PMETAC brushes between hydrophobic and hydrophilic configurations by ion exchange with ClO4 - and polyphosphate anions. This continuously variable regulation enabled control of the speed in an accurate and predictable manner and an autonomous response to the local chemical environment. This study suggests that the integration of polymer brushes with precisely adjustable responsiveness offers a promising route for motion control of smart MNMs that act like their counterparts in living systems.

Shape-Transformable, Fusible Rodlike Swimming Liquid Metal Nanomachine.

The T-1000 liquid metal terminator, which can transform and self-repair, represents a dream for decades that robots can fundamentally change our daily life. Until now, some large-scale liquid metal machines have been developed. However, there is no report on nanoscaled liquid metal machines and their biomedical applications. We describe here a shape-transformable and fusible rodlike swimming liquid metal nanomachine, based on the biocompatible and transformable liquid metal gallium. These nanomachines were prepared by a pressure-filter-template technology, and the diameter and length could be controlled by adjusting the nanoporous templates, filter time, and pressure. The as-prepared liquid gallium nanomotors display a core-shell nanorod structure composed of a liquid gallium core and solid gallium oxide shell. Upon exposure to an ultrasound field, the generated acoustic radiation force in the levitation plane can propel them to move autonomously. The liquid metal nanomachine can actively seek cancer cells and transform from a rod to a droplet after drilling into cells owing to the removal of gallium oxide layers in the acidic endosomes. These transformed nanomachines could fuse together inside cells and photothermally kill cancer cells under illumination of near-infrared light. Such acoustically propelled shape-transformable rodlike liquid metal nanomachines have great potential for biomedical applications.

Polybenzoxazole Nanofiber-Reinforced Moisture-Responsive Soft Actuators.

Hydromorphic biological systems, such as morning glory flowers, pinecones, and awns, have inspired researchers to design moisture-sensitive soft actuators capable of directly converting the change of moisture into motion or mechanical work. Here, we report a moisture-sensitive poly(p-phenylene benzobisoxazole) nanofiber (PBONF)-reinforced carbon nanotube/poly(vinyl alcohol) (CNT/PVA) bilayer soft actuator with fine performance on conductivity and mechanical properties. The embedded PBONFs not only assist CNTs to form a continuous, conductive film, but also enhance the mechanical performance of the actuators. The PBONF-reinforced CNT/PVA bilayer actuators can unsymmetrically adsorb and desorb water, resulting in a reversible deformation. More importantly, the actuators show a pronounced increase of conductivity due to the deformation induced by the moisture change, which allows the integration of a moisture-sensitive actuator and a humidity sensor. Upon changing the environmental humidity, the actuators can respond by the deformation for shielding and report the humidity change in a visual manner, which has been demonstrated by a tweezer and a curtain. Such nanofiber-reinforced bilayer actuators with the sensing capability should hold considerable promise for the applications such as soft robots, sensors, intelligent switches, integrated devices, and material storage.