Influence of elevated temperature on the species and mobility of chromium in ferrous sulfate-amended contaminated soil.

Ferrous sulfate (FeSO4) combined with acid pretreatment is usually employed to remediate contaminated soils containing Cr(VI). However, the long-term efficiency of this stabilization method is important for its sustainability. In this study, a gradient temperature-elevating exposure test was employed to investigate the stability of Cr in FeSO4-remediated soil when exposed to elevated temperatures (40 °C, 120 °C, and 500 °C), possibly caused by hot weather and/or wildfires. The results of chemical extraction and X-ray absorption near edge structure spectroscopy (XANES) showed that the Cr(VI) in contaminated soil was successfully transformed to Cr(III) after stabilization, resulting in the dramatic decrease of water-leachable Cr(VI). The stabilization efficiency was further improved under 40 °C treatment after 30 days. Subsequently, the 120 °C treatment (7 days) had relatively little effect on the Cr speciation and mobility in soils. However, even one day of 500 °C calcination resulted in the deterioration of stabilization efficiency, and the water-leachable Cr(VI) re-increased and became higher than the Chinese environmental standards (total Cr 15 mg/L, Cr(VI) 5 mg/L) for the classification of hazardous solid wastes. XANES results reflected that heating at 500 °C facilitate the formation of Cr2O3, which was mainly caused by thermal decomposition and dehydration of Cr(OH)3 in the soil. Besides, the transformation of Cr species resulted in the enhanced association of Cr with the most stable residual fraction (88.3%-91.6%) in soil. Based on chemical extraction results, it was suggested that the oxidation of Cr(III) to Cr(VI) contributed to the re-increased mobility of Cr(VI) in soil. However, the XANES results showed that almost no significant re-oxidization of Cr(III) to Cr(VI) happened after heating at 500 °C, which was probably caused by XANES linear combination fits (LCF) uncertainties. Moreover, the changes in soil properties, including a rise in pH to a slightly alkaline range and/or the decomposition of organic matter, possibly contributed to the enhanced mobility of Cr(VI) in soil. This study contributes to clarifying the mobility and transformation of Cr in contaminated soils and provides a support for the sustainable management of remediated soils.

Enhanced Oxidation of Antibiotics by Ferrate Mediated with Natural Organic Matter: Role of Phenolic Moieties.

The increasing presence of antibiotics in water sources threatens public health and ecosystems. Various treatments have been previously applied to degrade antibiotics, yet their efficiency is commonly hindered by the presence of natural organic matter (NOM) in water. On the contrary, we show here that nine types of NOM and NOM model compounds improved the removal of trimethoprim and sulfamethoxazole by ferrate(VI) (FeVIO42-, Fe(VI)) under mild alkaline conditions. This is probably associated with the presence of phenolic moieties in NOMs, as suggested by first-order kinetics using NOM, phenol, and hydroquinone. Electron paramagnetic resonance reveals that NOM radicals are generated within milliseconds in the Fe(VI)-NOM system via single-electron transfer from NOM to Fe(VI) with the formation of Fe(V). The dominance of the Fe(V) reaction with antibiotics resulted in their enhanced removal despite concurrent reactions between Fe(V) and NOM moieties, the radicals, and water. Kinetic modeling considering Fe(V) explains the enhanced kinetics of antibiotics abatement at low phenol concentrations. Experiments with humic and fulvic acids of lake and river waters show similar results, thus supporting the enhanced abatement of antibiotics in real water situations.

Growth, physiological, and temperature characteristics in chinese cabbage pakchoi as affected by Cd- stressed conditions and identifying its main controlling factors using PLS model.

BACKGROUND: Although hormesis induced by heavy metals is a well-known phenomenon, the involved biological mechanisms are not fully understood. Cadmium (Cd) is a prevalent heavy metal in the environment. Exposure of Cd, via intake or consumption of Cd-contaminated air or food, poses a huge threat to human health. Chinese cabbage pakchoi (Brassica chinensis L.) is widely planted and consumed as a popular vegetable in China. Therefore, studying the response of Chinese cabbage pakchoi to Cd- stressed conditions is critical to assess whether cabbage can accumulate Cd and serve as an important Cd exposure pathway to human beings. In this study, we investigated the influence of Cd stress on growth, photosynthetic physiology, antioxidant enzyme activities, nutritional quality, anatomical structure, and canopy temperature in Chinese cabbage pakchoi. A partial least squares (PLS) model was used to quantify the relationship between physical and chemical indicators with Cd accumulation in cabbage, and identify the main controlling factors. RESULTS: Results showed that Cd stress significantly inhibited cabbage's growth and development. When Cd stress was increased, the phenotypic indicators were significantly reduced. Meanwhile, Cd stress significantly enhanced the oxidative stress response of cabbage, such as the activities of catalase (CAT), superoxide dismutase (SOD), peroxidase (POD), ascorbate peroxidase (APX), and the content of malondialdehyde (MDA) in leaves. Such a change tended to increase fenestrated tissues' thickness but decrease the thickness of leaf and spongy tissues. Moreover, Cd stress significantly increased soluble sugar, protein, and vitamin C contents in leaves as well as the temperature in the plant canopy. The PLS model analysis showed that the studied phenotypic and physicochemical indicators had good relationships with Cd accumulation in roots, shoots, and the whole plant of cabbage, with high coefficient of determination (R2) values of 0.891, 0.811, and 0.845, and low relative percent deviation (RPD) values of 3.052, 2.317, and 2.557, respectively. Furthermore, through analyzing each parameter's variable importance for projection (VIP) value, the SOD activity was identified as a key factor for indicating Cd accumulation in cabbage. Meanwhile, the effects of CAT on Cd accumulation in cabbage and the canopy mean temperature were also high. CONCLUSION: Cd stress has significant inhibitory effects and can cause damage cabbage's growth and development, and the SOD activity may serve as a key factor to indicate Cd uptake and accumulation in cabbage.

Designing Magnesium Phosphate Cement for Stabilization/Solidification of Zn-Rich Electroplating Sludge.

Electroplating sludge is a hazardous waste due to its high potential to leach toxic elements into the natural environment. To alleviate this issue, we tailored magnesium phosphate cement (MPC) as a low-carbon material for stabilization/solidification (S/S) of Zn-rich electroplating sludge. The interaction between MPC and ZnO was investigated to clarify the precipitate chemistry, microstructure transition, and chemical environment of Zn species in the MPC-treated Zn sludge system. Comprehensive characterization (by X-ray diffraction (XRD), 31P nuclear magnetic resonance (NMR), and extended X-ray absorption fine structure spectroscopy (EXAFS)) and thermodynamic modeling results revealed that the incorporated ZnO preferentially reacted with phosphate to form Zn3(PO4)2·2H2O/Zn3(PO4)2·4H2O, changing the orthophosphate environment in the MPC system. Stronger chemical bonding between Zn and phosphate in comparison to the bonding between Mg and phosphate also resulted in the formation of amorphous Zn3(PO4)2·2H2O/Zn3(PO4)2·4H2O. Zn3(PO4)2·4H2O precipitate appears to predominate at high {K+}{H+}{HPO42-} values, and the formation of Zn3(PO4)2·2H2O/Zn3(PO4)2·4H2O competed for the Mg sites in the MPC system, leading to the inhibition of formation of Mg-phosphate precipitates. Overall, this work uncovers the precipitate chemistry and microstructure transition of Zn species in the MPC system, providing new insights into the sustainable S/S of Zn-contaminated wastes by adopting MPC.

Immobilization mechanism of cesium in geopolymer: Effects of alkaline activators and calcination temperature.

Geopolymer is always regarded as a promising material for the immobilization of radioactive waste. In the present study, the stabilization of Cs in geopolymers activated by NaOH and Na2SiO3 solutions and calcined at various temperatures was studied via toxicity characteristic leaching procedure (TCLP), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope and energy dispersive spectroscopy (SEM-EDS), solid-state nuclear magnetic resonance (SSNMR), and N2 adsorption-desorption isotherm. For both NaOH-activated and Na2SiO3-activated geopolymers, the leaching concentrations of Cs decreased with the increase of calcination temperature. Specifically, most of the amorphous substance was crystallized to nepheline at 1000 °C for NaOH-activated geopolymer, and Cs+ can be incorporated into the structure of nepheline, contributing to the reduction of Cs leaching concentration. However, the amorphous structure was still maintained for Na2SiO3-activated geopolymer even after calcination at 1000 °C. It has been deduced that the main structure of Na2SiO3-activated geopolymer after calcination at 1000 °C should be in short-range order and Cs+ can be locked in a micro "crystal" structure. In addition, the change of specific surface area was not fully consistent with the decreasing trend of Cs leaching concentration. Therefore, the inner structure and the specific surface area of geopolymer should have a combined effect on the leaching behavior of Cs. This study can provide new insights into the application of geopolymer to immobilize radionuclides.

Green synthesis of ceramsite from industrial wastes and its application in selective adsorption: Performance and mechanism.

The increasing requirement and consumption of coal has resulted in a large accumulation of coal gangue. The reuse and recycling of coal gangue have become a high priority for sustainable development. A sustainable and efficient ceramsite adsorbent was prepared for copper ions adsorption by using coal gangue, coal fly ash, and copper slag as the main materials. The appropriate performance of the ceramsite could be obtained at a mixture of coal gangue, coal fly ash, and copper slag at a weight ratio of 3:4:1. The optimal sintering temperature and time were 1050 °C and 20 min, respectively. The main crystalline phases of ceramsite were quartz, mullite, and anorthite. Many micropores are connecting the interior on the surface of ceramsite under scanning electron microscope. The maximum copper ions adsorption capacity reached up to 20.6 mg/g at 303 K when pH and time were 5 and 1440 min, respectively. The adsorption kinetics and isotherm could be described by the pseudo-second-order model and Freundlich model, respectively. The adsorption mechanisms of Cu2+ with ceramsite were attributed to Cu(OH)2 precipitation formed on the alkaline surface of ceramsite and complexation reactions occurred between the O-containing groups (including C-O, Fe-O, and Si-O) from ceramsite and Cu2+. The prepared ceramsite may be also applied to other heavy metal wastewater treatments.

Elucidating the Role of Dissolved Organic Matter and Sunlight in Mediating the Formation of Ag-Au Bimetallic Alloy Nanoparticles in the Aquatic Environment.

Elucidating the interactions between metal ions and dissolved organic matter and deciphering mechanisms for their mineralization in the aquatic environment are central to understanding the speciation, transport, and toxicity of nanoparticles (NPs). Herein, we examine the interactions between Ag+ and Au3+ ions in mixed solutions (χAg = 0.2, 0.5, and 0.8) in the presence of humic acids (HAs) under simulated sunlight; these conditions result in the formation of bimetallic Ag-Au NPs. A key distinction is that the obtained alloy NPs are compositionally and morphologically rather different from NPs obtained from thermally activated dark processes. Photoillumination triggers a distinctive plasmon-mediated process for HA-assisted reductive mineralization of ions to bimetallic alloy NPs which is not observed in its dark thermal reduction counterpart. The initial nucleation of bimetallic NPs is dominated by differences in the cohesive energies of Ag and Au crystal lattices, whereas the growth mechanisms are governed by the strongly preferred incorporation of Ag ions, which stems from their greater photoreactivity. The bimetallic NPs crystallize in shapes governed by the countervailing influence of minimizing free energy through the adoption of Wulff constructions and the energetic penalties associated with twin faults. As such, assessments of the stability and the potential toxic effects of bimetallic NPs arising from their possible existence in aquatic environments will depend sensitively on the origins of their formation.

Co-sorption of Sr2+ and SeO42- as the surrogate of radionuclide by alginate-encapsulated graphene oxide-layered double hydroxide beads.

Graphene oxides (GO) and layered double hydroxides (LDHs) were applied to produce alginate beads for the remove of 90Sr2+ and 79SeO42-. The Freundlich isotherm indicated that the Sr2+ sorptions were based on the energetically heterogeneous multilayer surfaces. In contrast, the sorption behavior of SeO42- fitted to the Langmuir adsorption isotherm models, indicating that the removal of SeO42- was caused by the ion-exchange of LDHs. The synthesized LDH/GO alginates beads were also applied for setting up small-bore adsorption columns with loading synthetic SeO42- and Sr2+ contaminated wastewater. Based on the water chemistry, the adsorbed amount of Sr2+ significantly increased after using alginates beads, which was attributed to the functional groups of either GO or alginic acid. The incorporated SeO42- was highly depended on the contents of fabricated LDHs in alginate beads. Specifically, the adsorption capacity of Sr2+ (0.85-0.91 mmol/g) on GO slightly increased after alginates fabrication. Therefore, it was deduced that this layered material was partially exfoliated during the manufacture and thus increased the sorption sites. Applications of LDH/GO alginates beads in the removal of both Sr2+ and SeO42- in water and soil treatment have a significant impact on the environmental remediation.

Recent advances of SBA-15-based composites as the heterogeneous catalysts in water decontamination: A mini-review.

As an emerging class of silica-based mesoporous materials with incorporation of active components (e.g., transition metals/metal oxides and nanocarbons), SBA-15-based composites (X@SBA-15) have been attracting increasing attention in the field of water treatment owing to their unique characteristics and excellent remediation performance. This paper reviews recent advances in catalytic applications of X@SBA-15 to remove organic contaminants from water. Emphasis is made on the use of X@SBA-15 in four advanced oxidation processes (AOPs) (i.e., photocatalysis, Fenton-like oxidation, catalytic ozonation, and sulfate radical-based oxidation). Impregnation and hydrothermal methods are two most widely used synthetic approaches to combine the active composites with SBA-15, obtaining a synergistic effect with significant improvement in their individual catalytic activity for pollution remediation. The enhanced generation of highly reactive hydroxyl radicals from the surface of X@SBA-15 was widely recognized as being responsible for water decontamination using these AOPs, while sulfate radicals were also involved during activation of persulfate or peroxymonosulfate. Especially, X@SBA-15 could significantly enhance the light harvest and reduce the recombination of photo-induced electrons and holes during photocatalytic treatment, which also played the critical role in oxidizing the organics. The superior catalytic performance of X@SBA-15 without leaching metal ions during successive runs demonstrated the excellent reusability and structural stability. Together with the reduced toxicity of the treated solutions and the cost-effective characteristics of X@SBA-15 nanohybrids reported in the published literature, their great potential as the efficient and environmentally friendly heterogeneous catalysts in a real use scenario is suggested. Finally, the future perspectives on the development and practical utilization of X@SBA-15 are addressed.

Attachment of cerium oxide nanoparticles of different surface charges to kaolinite: Molecular and atomic mechanisms.

Sustainable applications of nanotechnology in agriculture require insights into the interactions between engineered nanoparticles (ENPs) and clay minerals, a key component in soil that governs the soil properties and functions. This study investigated the charge-dependent interactions of cerium oxide nanoparticles (CeO2NPs) with kaolinite at atomic level with several complementary surface characterization techniques. High resolution transmission electron microscope (HRTEM) and atomic force microscope (AFM) images showed strong attachment of positively charged and neutral CeO2NPs to the surface of kaolinite while the negatively charged CeO2NPs demonstrated low affinity to the surface of kaolinite, indicating strong electrostatic interactions between CeO2NPs and kaolinite surface. Attached CeO2NPs on kaolinite surface displayed charge-dependent aggregation, with neutral CeO2NPs showing the most substantial aggregation on kaolinite surface. The variation in hydrodynamic size and surface charge of kaolinite with the charge on CeO2NPs was observed. The attachment of CeO2NPs also changed the surface charge density distribution on the surface of kaolinite, converting a relatively homogenously charged basal plane into a heterogeneously charged plate. The change on kaolinite surface charge density may markedly affect the interactions of clay minerals with surrounding macro- and micro-nutrients in soil pore water and affect their bioavailability to plants.

Enhanced adsorption of aqueous perfluorooctanoic acid on iron-functionalized biochar: Elucidating the roles of inner-sphere complexation.

Perfluorooctanoic acid (PFOA) is ubiquitously detected in various water bodies, which raises the urgent need for developing effective and economic remediation methods in response to its health risks. The adsorptive removal of PFOA by biochar (BC) is regarded as a simple, effective, and economical technique. However, engineered BCs, including FeCl3-activated BC, for PFOA removal and adsorption mechanisms have been ill-studied. In this study, a FeCl3-activated dairy manure-derived biochar (Fe@MBC) was prepared via one-step pyrolysis/activation, and its properties and adsorption characteristics were compared with a pristine manure-derived biochar (P-MBC). The FeCl3 activation largely increased the surface area of Fe@MBC and the deposition of FexOy minerals on surface of Fe@MBC while significantly elevating the surface roughness of Fe@MBC. The maximum adsorption capacity of Fe@MBC for PFOA (233 mg·g-1) was five times higher than that of P-MBC (46 mg·g-1). PFOA adsorption was favorable at low solution pH and was independent on ionic strength, which supported the major contribution by inner-sphere complexation rather than out-sphere complexation. This mechanism was further confirmed by the disappearance of FeO peak on Fourier transform infrared spectrum and the blue-shift of Fe binding energies on X-ray photoelectron Fe 2p spectrum of Fe@MBC after PFOA adsorption. Fe@MBC maintained a near 100 % adsorption capacity for PFOA after 3 cycles of chemical regeneration. Fe@MBC also exhibited efficient removal for PFOA and other PFAS compounds at trace levels in the lake water and dairy effluent. Thus, this study highlights a promising insight for selectively eliminating PFASs from water.

Increased dependence on nitrogen-fixation of a native legume in competition with an invasive plant.

Suppression of roots and/or their symbiotic microorganisms, such as mycorrhizal fungi and rhizobia, is an effective way for alien plants to outcompete native plants. However, little is known about how invasive and native plants interact with the quantity and activity of nutrient-acquisition agents. Here a pot experiment was conducted with monoculture and mixed plantings of an invasive plant, Xanthium strumarium, and a common native legume, Glycine max. We measured traits related to root and nodule quantity and activity and mycorrhizal colonization. Compared to the monoculture, fine root quantity (biomass, surface area) and activity (root nitrogen (N) concentration, acid phosphatase activity) of G. max decreased in mixed plantings; nodule quantity (biomass) decreased by 45%, while nodule activity in N-fixing via rhizobium increased by 106%; mycorrhizal colonization was unaffected. Contribution of N fixation to leaf N content in G. max increased in the mixed plantings, and this increase was attributed to a decrease in the rhizosphere soil N of G. max in the mixed plantings. Increased root quantity and activity, along with a higher mycorrhizal association was observed in X. strumarium in the mixed compared to monoculture. Together, the invasive plant did not directly scavenge N from nodule-fixed N, but rather depleted the rhizosphere soil N of the legume, thereby stimulating the activity of N-fixation and increasing the dependence of the native legume on this N source. The quantity-activity framework holds promise for future studies on how native legumes respond to alien plant invasions.

Battery-Type-Behavior-Retention Ni(OH)2-rGO Composite for an Ultrahigh-Specific-Capacity Asymmetric Electrochemical Capacitor Electrode.

Nanosized battery-type materials applied in electrochemical capacitors can effectively reduce a series of problems caused by low conductivity and large volume changes. However, this approach will lead to the charging and discharging process being dominated by capacitive behavior, resulting in a serious decline in the specific capacity of the material. By controlling the material particles to an appropriate size and a suitable number of nanosheet layers, the battery-type behavior can be retained to maintain a large capacity. Here, Ni(OH)2, which is a typical battery-type material, is grown on the surface of reduced graphene oxide to prepare a composite electrode. By controlling the dosage of the nickel source, the composite material with an appropriate Ni(OH)2 nanosheet size and a suitable number of layers was prepared. The high-capacity electrode material was obtained by retaining the battery-type behavior. The prepared electrode had a specific capacity of 397.22 mA h g-1 at 2 A g-1. After the current density was increased to 20 A g-1, the retention rate was as high as 84%. The prepared asymmetric electrochemical capacitor had an energy density of 30.91 W h kg-1 at a power density of 1319.86 W kg-1 and the retention rate could reach 79% after 20,000 cycles. We advocate an optimization strategy that retains the battery-type behavior of electrode materials by increasing the size of nanosheets and the number of layers, which can significantly improve the energy density while combining the advantage of the high rate capability of the electrochemical capacitor.

Strategy of Voltage Match on the Maximum Power Point for a High-Efficiency Photorechargeable Device.

A photorechargeable device can generate power from sunlight and store it in one device, which has a broad application prospect in the future. However, if the working state of the photovoltaic part in the photorechargeable device deviates from the maximum power point, its actual power conversion efficiency will reduce. The strategy of voltage match on the maximum power point is reported to achieve a high overall efficiency (ηoa) of the photorechargeable device assembled by a passivated emitter and rear cell (PERC) solar cell and Ni-based asymmetric capacitors. According to matching the voltage of the maximum power point of the photovoltaic part, the charging characteristics of the energy storage part are adjusted to realize a high actual power conversion efficiency of the photovoltaic part (ηpv). The ηpv of a Ni(OH)2-rGO-based photorechargeable device is 21.53%, and the ηoa is up to 14.55%. This strategy can promote further practical application for the development of photorechargeable devices.

[Effects of Polystyrene Microplastics on Growth, Physiology, Biochemistry, and Canopy Temperature Characteristics of Chinese Cabbage Pakchoi (Brassica chinensis L.)].

The aim of this study was to clarify the response characteristics of Chinese cabbage pakchoi (Brassica chinensis L.) under two particle size (100 nm and 1000 nm) polystyrene microplastic (PS-MPs) stress conditions. This study can provide a theoretical basis and experimental reference for the interpretation of the physiological and ecological mechanism of microplastic pollution and the bioremediation of microplastic-contaminated soil. Hydroponic experiments were carried out to study the effects of two particle sizes (100 nm and 1000 nm) of PS-MPs on growth, photosynthetic physiology, antioxidant enzyme activities, nutritional quality, anatomical structure, and canopy temperature in Chinese cabbage pakchoi. The results showed that PS-MPs stress significantly inhibited the growth and development of Chinese cabbage pakchoi. When PS-MPs stress was increased, the phenotypic indicators were significantly reduced. Meanwhile, PS-MPs stress significantly enhanced the oxidative stress response of Chinese cabbage pakchoi, such as the activities of catalase (CAT), peroxidase (POD), superoxide dismutase (SOD), and ascorbate peroxidase (APX) and the content of malondialdehyde (MDA) in leaves. Such a change tended to decrease the thickness of fenestrated and leaf and spongy tissues. Moreover, PS-MPs stress significantly increased the canopy population temperature of the Chinese cabbage pakchoi leaves. Microplastic stress had obvious inhibitory effects and toxic damage on the growth, development, and physical and chemical properties of Chinese cabbage pakchoi.

Flooding and drainage induced abiotic reactions control metal solubility in soil of a contaminated industrial site.

Intense industrialization has led to the increasing leaching risk of metals into groundwater at heavily polluted industrial sites. However, metal dissolution in polluted industrial soils has been neither fully investigated nor quantified before. In this study, the dissolution of Zn, Ni, and Cu in soil from a heavily contaminated industrial site during a flooding-drainage period was investigated by sequential extraction, geochemical modelling, and X-ray absorption near edge structure spectroscopy. The results showed a steady decrease in metal solubility during both reduction and oxidation stages. During reduction, with limited decrease in Eh (>100 mV), formation of carbonate precipitates rather than sulfide precipitates and adsorption on soil solids was responsible for Zn and Ni dissolution, whereas bound to soil organic matter (SOM) and iron oxides dominated Cu dissolution, due to its lower concentration and higher affinity to SOM and iron oxides compared to Zn and Ni. During oxidation, the acidity caused by ferrous oxidation was buffered by calcite dissolution, while metal precipitation ceased and adsorption on soil surface controlled metal solubility. The metal solubility and speciation during the flooding-drainage process were quantitatively predicted by geochemical model. The findings demonstrate that due to high metal concentrations and weak microbial effect in the industrial soil, metal release was largely regulated by abiotic reactions rather than biotic reactions, which is somehow different from that of the wetland or rice field soils.

Zero valent iron or Fe3O4-loaded biochar for remediation of Pb contaminated sandy soil: Sequential extraction, magnetic separation, XAFS and ryegrass growth.

In this study, the feasibility of using zero-valent iron (ZVI) and Fe3O4-loaded biochar for Pb immobilization in contaminated sandy soil was investigated. A 180-day incubation study, combined with dry magnetic separation, chemical extraction, mineralogical characterization, and model plant (ryegrass, namely the Lilium perenne L.) growth experiment was conducted to verify the performance of these two materials. The results showed that both amendments significantly transferred the available Pb (the exchangeable and carbonates fraction) into more stable fractions (mainly Fe/Mn oxides-bound Pb), and ZVI alone showed a better performance than the magnetic biochar alone. The magnetic separation and extended X-ray absorption fine structure (EXAFS) analysis proved that Fe (oxyhydr)oxides on aged ZVI particles were the major scavengers of Pb in ZVI-amended soils. In comparison, the reduced Pb availability in magnetic biochar-amended soil could be explained by the association of Pb with Fe/Mn (oxyhydr)oxides in aged magnetic biochar, also the possible precipitation of soil Pb with soluble anions (e.g. OH-, PO43-, and SO42-) released from magnetic biochar. ZVI increased ryegrass production while Fe3O4-loaded biochar had a negative effect on the ryegrass growth. Moreover, both markedly decreased the Pb accumulation in aboveground and root tissues. The simple dry magnetic separation presents opportunities for the removal of Pb from soils, even though the efficiencies were not high (17.5% and 12.9% of total Pb from ZVI and biochar-treated soils, respectively). However, it should be noted that the ageing process easily result in the loss of magnetism of ZVI while the magnetic biochar tends to be more stable and has high retrievability during the dry magnetic separation application.

Designing novel magnesium oxysulfate cement for stabilization/solidification of municipal solid waste incineration fly ash.

Municipal solid waste incineration (MSWI) fly ash is a typical hazardous waste worldwide. In this study, an innovative magnesium oxysulfate cement (MOSC) binder was designed for stabilization/solidification (S/S) of MSWI fly ash, focusing on the interactions between MOSC binder and typical metallic cations (Pb2+)/oxyanions (AsO33-). Experimental results showed that Pb and As slightly inhibited the reaction of high-sulfate 5MS system but significantly suppressed the reaction process of low-sulfate 10MS system. The 5MS binder system exhibited excellent immobilization efficiencies (99.8%) for both Pb and As. The extended X-ray absorption fine structure spectra suggested that Pb2+ coordinated with SO42-/OH- in the MOSC system and substituted Mg2+ ion sites in the internal structure of 5Mg(OH)2·MgSO4.7H2O (5-1-7) phase. In contrast, the AsO33- substituted SO42- sites with the formation of inner-sphere complexes with Mg2+ in the large interlayer space of the 5-1-7 structure. Subsequent MSWI fly ash S/S experiments showed that a small amount of reactive Si in MSWI fly ash interfered with the MOSC reaction and adversely influenced the immobilization efficiencies of Pb, As, and other elements. Through the use of 33 wt% tailored MOSC binder for MSWI fly ash treatment, a satisfying S/S performance could be achieved.

Cytotoxicity of stabilized/solidified municipal solid waste incineration fly ash.

Low-carbon stabilization/solidification (S/S) is of increasing importance as an option for the treatment of municipal solid waste incineration fly ash (MIFA). This study tailored four binders (e.g., ordinary Portland cement (OPC), calcium aluminate cement (CAC), phosphate-modified OPC, and phosphate-modified CAC) for S/S of MIFA and evaluated the cytotoxicity of treated MIFA by using A549 cell-based in-vitro assay. After S/S treatment, the leachability of Cr, Cu, Zn and Pb from MIFA decreased by 76.1%, 93.4%, 69.6%, and 85.5%, respectively. Spectroscopic analysis indicated that the hydration products determined the immobilization efficiencies of various binders, and strong bonding between metallic cations and phosphate enhanced the immobilization efficiency. The treated MIFA showed significantly lower cellular reactive oxygen species (ROS)-inducing abilities than original MIFA, in which with phosphate-modified OPC treated MIFA showed the lowest ROS levels. Intracellular ROS and multicytotoxicity results also revealed that the treated MIFA not only decreased the cytotoxicity-inducing capability but also enhanced the tolerant dosage of cytotoxicity, in which phosphate-modified S/S treatments showed more effective mitigation (25% less cytotoxicity) than plain cement treatments due to the high-efficiency immobilization of potentially toxic elements. This study develops a pioneering assessment protocol to measure the success of sustainable treatment of MIFA in human health perspective.