Fe Crystalline Phases in Fe/C Composites Modulated the Selective Adsorption of Pb(II) from Industrial Wastewater with Cd(II): An Electronic-Scale Perspective.

Fe oxide or Fe0-based materials display weak removal capacity for Pb(II), especially in the presence of Cd(II), and the electronic-scale mechanisms are not reported. In this study, Fe3C(220) modified black carbon (BC) [Fe3C(220)@BC] with high adsorption and selectivity for Pb(II) from industrial wastewater with Cd(II) was developed. The quantitative experiment suggested that Fe species accounted for 80.5-100 and 18.4-33.8% of Pb(II) and Cd(II) removal, respectively. Based on X-ray absorption near-edge structure analysis, 57.3% of adsorbed Pb2+ was reduced to Pb0; however, 61.6% of Cd2+ existed on Fe3C@BC. Density functional theory simulation unraveled that Cd(II) adsorption was attributed to the cation-π interaction with BC, whereas that of Pb(II) was ascribed to the stronger interactions with different Fe phases following the order: Fe3C(220) > Fe0(110) > Fe3O4(311). Crystal orbital bond index and Hamilton population analyses were innovatively applied in the adsorption system and displayed a unique discovery: the stronger Pb(II) adsorption on Fe phases was mediated by a combination of covalent and ionic bonding, whereas ionic bonding was mainly accounted for Cd(II) adsorption. These findings open a new chapter in understanding the functions of different Fe phases in mediating the fate and transport of heavy metals in both natural and engineered systems.

Pyrite-stimulated bio-reductive immobilization of perrhenate: Insights from integrated biotic and abiotic perspectives.

Microbes possessing electron transfer capabilities hold great promise for remediating subsurface contaminated by redox-active radionuclides such as technetium-99 (99TcO4-) through bio-transformation of soluble contaminants into their sparingly soluble forms. However, the practical application of this concept has been impeded due to the low electron transfer efficiency and long-term product stability under various biogeochemical conditions. Herein, we proposed and tested a pyrite-stimulated bio-immobilization strategy for immobilizing ReO4- (a nonradioactive analogue of 99TcO4-) using sulfate-reducing bacteria (SRB), with a focus on pure-cultured Desulfovibrio vulgaris. Pyrite acted as an effective stimulant for the bio-transformation of ReO4-, boosting the removal rate of ReO4- (50 mg/L) in a solution from 2.8 % (without pyrite) to 100 %. Moreover, the immobilized products showed almost no signs of remobilization during 168 days of monitoring. Dual lines of evidence were presented to elucidate the underlying mechanisms for the pyrite-enhanced bio-activity. Transcriptomic analysis revealed a global upregulation of genes associated with electron conductive cytochromes c network, extracellular tryptophan, and intracellular electron transfer units, leading to enhanced ReO4- bio-reduction. Spectroscopic analysis confirmed the long-term stability of the bio-immobilized products, wherein ReO4- is reduced to stable Re(IV) oxides and Re(IV) sulfides. This work provides a novel green strategy for remediation of radionuclides- or heavy metals-contaminated sites.

Ti3C2 mediates the NiFe-LDH layered electrocatalyst to enhance the OER performance for water splitting.

Oxygen evolution reaction (OER) is a very complex process with slow reaction kinetics and high overpotential, which is the main limitation for the commercial application of water splitting. Thus, it is of necessary to design high-performance OER catalysts. NiFe based layered double hydroxides (NiFe-LDHs) have recently gained a lot of attention due to their high reaction activity and simple manufacturing process. In this study, a novel electrocatalyst based on NiFe-LDH was constructed by introducing Ti3C2, which was utilized to modulate the structural and electronic properties of the electrocatalysts. Structural examinations reveal that the Ti3C2 of 2D structure successfully dope the NiFe-LDHs nanosheets, forming NiFe-LDH/Ti3C2 heterojunctions. Firstly, the heterojunction substantially reduces the charge transfer resistance, promoting the electron migration between the LDH nanosheets. Secondly, theoretical calculations demonstrate that the energy barrier between the rate-determining step from *OH to *O is lowered, favoring the formation of the reaction intermediates and thus the occurrence of OER. As a result, the composite electrocatalyst exhibits a low overpotential of 334 mV at a current density of 10 mA/cm2 and a small Tafel slope of 55 mV/dec, which are superior to those of the NiFe-LDH by 11.2 % and 38.5 %, respectively. This study provides inspiration for promoting the performances of NiFe based electrocatalysts by utilizing 2D materials.

Two-Dimensional SnS Mediates NiFe-LDH-Layered Electrocatalyst toward Boosting OER Activity for Water Splitting.

NiFe-layered double hydroxides (NiFe-LDHs), as promising electrocatalysts, have received significant research attention for hydrogen and oxygen generation through water splitting. However, the slow oxidation kinetics of NiFe-LDH, due to the limited number of active sites and the low conductivity, hinders the improvement of the water-splitting efficiency. Therefore, to overcome the obstacles, two-dimensional (2D) SnS was first explored to tailor the prepared NiFe-LDH via the hydrothermal method. A NiFe-LDH/SnS heterojunction is built, which is observed from the microstructural investigations. SnS incorporation could greatly improve the conductivity of the NiFe-LDH sheets, which was reflected by the reduced charge transfer resistance. Moreover, SnS layers modulated the electronic environment around the active sites, favoring the adsorption of intermediates during the oxygen evolution reaction (OER) process, which was verified by density functional theory calculations. A synergistic effect induced by the NiFe-LDH/SnS heterostructure promoted the OER activities in electrical, electronic, and energetic aspects. Consequently, the as-prepared NiFe-LDH/SnS electrocatalyst greatly improved the electrocatalytic performance, exhibiting 20% and 27% reductions in the overpotential and Tafel slope compared with those of pristine NiFe-LDH, respectively. The results provide a strategy for regulating NiFe-based electrocatalysts by using emerging 2D materials to enhance water-splitting efficiency.

Aqueous and solid phase photocatalytic degradation of perfluorooctane sulfonate by carbon- and Fe-modified bismuth oxychloride.

In this study, we prepared and tested a carbon-modified, Fe-loaded bismuth oxychloride (Fe-BiOCl/CS) photocatalyst for photocatalytic degradation of perfluorooctane sulfonate (PFOS). Structural analyses revealed a (110) facet-dominated sheet-type BiOCl crystal structure with uniformly distributed Fe and confirmed carbon modification of the photocatalyst. The presence of d-glucose facilitated the growth control of BiOCl particles and enhanced the adsorption of PFOS via added hydrophobic interaction. Adsorption kinetic and equilibrium tests showed rapid uptake rates of PFOS and high adsorption capacity with a Langmuir Qmax of 1.51 mg/g. When used for directly treating PFOS in solution, Fe-BiOCl/CS was able to mineralize or defluorinate 83% of PFOS (C0 = 100 µgL-1) under UV (254 nm, intensity = 21 mW cm-2) in 4 h; and when tested in a two-step mode, i.e., batch adsorption and subsequent photodegradation, Fe-BiOCl/CS mineralized 65.34% of PFOS that was pre-concentrated in the solid phase under otherwise identical conditions; while the total degradation percentages of PFOS were 83.48% and 80.50%, respectively, for the two experimental modes. The photoactivated electrons and/or hydrated electrons and superoxide radicals primarily initiated the desulfonation of PFOS followed by decarboxylation and defluorination, through a stepwise chain-subsiding mechanism. The elevated photocatalytic activity can be attributed to the effective separation of e-/h+ pairs facilitated by the (110) interlayer electrostatic field, Fe doping, and the presence of oxygen vacancies. This work reveals the potential of carbon-modified and Fe-co-catalyzed BiOCl for concentrating and degrading PFOS and possibly other persistent organic pollutants.

Application of apatite particles for remediation of contaminated soil and groundwater: A review and perspectives.

With rapid industrial development and population growth, the pollution of soil and groundwater has become a critical concern all over the world. Yet, remediation of contaminated soil and water remains a major challenge. In recent years, apatite has gained a surging interest in environmental remediation because of its high treatment efficiency, low cost, and environmental benignity. This review summarizes recent advances in: (1) natural apatite of phosphate ores and biological source; (2) synthesis of engineered apatite particles (including stabilized or surface-modified apatite nanoparticles); (3) treatment effectiveness of apatite towards various environmental pollutants in soil and groundwater, including heavy metals (e.g., Pb, Zn, Cu, Cd, and Ni), inorganic anions (e.g., As oxyanions and F-), radionuclides (e.g., thorium (Th), strontium (Sr), and uranium (U)), and organic pollutants (e.g., antibiotics, dyes, and pesticides); and (4) the removal and/or interaction mechanisms of apatite towards the different contaminants. Lastly, the knowledge or technology gaps are identified and future research needs are proposed.

Effects of abiotic mineral transformation of FeS on the dynamic immobilization of Cr(VI) in oxic aquatic environments.

Iron sulfide (FeS) can reductively convert soluble Cr(VI) into insoluble Cr(III) under anoxic conditions. However, the fate and transformation of FeS and the stability of immobilized Cr under various oxic environmental conditions are poorly understood. The results show that FeS transforms into pyrrhotite and pyrite intermediates principally and finally lepidocrocite and elemental sulfur, accordingly accounting for 66.1% and 33.9%. Temperature, fulvic acid as natural organic matter and coexisted ions of nitrate, bicarbonate, and calcium affect the evolution of FeS insignificantly. Transformation of FeS involves surface-mediated oxidation of FeS solids, and minor proton-promoted dissolution and oxidation, accompanying synergistic oxidation of Fe(II) and S(-II). Cr(VI) removal performances of oxygenated FeS with increasing duration showed a rise-fall trend. Reduction dominates Cr(VI) uptake first and finally, sorption prevails with the gradual FeS oxygenation. Cr(VI) removal correlates linearly with Cr(VI) reduction, and the reduced Cr species can be predicted based on the known Cr(VI) removal performance. As the FeS oxygenation time increases, newly generated pyrite improves Cr(VI) reduction and removal, and then a decreasing ability to reduce Cr(VI) causes a drop in Cr(VI) removal. These findings provide new insight into the oxidative transformation of FeS in oxic aquatic environments and its impact on Cr(VI) levels.

Application potential of zero-valent aluminum in nitrophenols wastewater decontamination: Enhanced reactivity, electron selectivity and anti-passivation capability.

Nitrophenols (NPs) are highly toxic and easy to accumulate to high concentrations (> 500 mg/L) in real wastewater. The nitro group contained in NPs is an electron-absorbing group that is easy to reduce and difficult to oxidize, so there is an urgent need to develop reduction removal technology. Zero-valent aluminum (ZVAl) is an excellent electron donor that can reductively transform various refractory pollutants. However, ZVAl is prone to rapid deactivation due to non-selective reactions with water, ions, etc. To overcome this critical limitation, we prepared a new type of carbon nanotubes (CNTs) modified microscale ZVAl, CNTs@mZVAl, through a facile mechanochemical ball milling method. CNTs@mZVAl had outstanding high reactivity in degrading p-nitrophenol even 1000 mg/L and showed up to 95.50% electron utilization efficiency. Moreover, CNTs@mZVAl was highly resistant to the passivation by dissolved oxygen, ions and natural organic matters coexisting in water matrix, and remained highly reactive after aging in the air for 10 days. Furthermore, CNTs@mZVAl could effectively remove dinitrodiazophenol from real explosive wastewater. The excellent performance of CNTs@mZVAl is due to the combination of selective adsorption of NPs and CNTs-mediated e-transfer. CNTs@mZVAl looks promising for the efficient and selective degradation of NPs, with broader prospects for real wastewater treatment.

Poly- and Perfluoroalkyl Substances (PFAS) in Landfills: Occurrence, Transformation and Treatment.

Landfills have served as the final repository for > 50 % municipal solid wastes in the United States. Because of their widespread uses and persistence in the environment, per- and polyfluoroalkyl substances (PFAS) (>4000 on the global market) are ubiquitously present in everyday consumer, commercial and industrial products, and have been widely detected in both closed (tens ng/L) and active (thousands to ten thousands ng/L) landfills due to disposal of PFAS-containing materials. Along with the decomposition of wastes in-place, PFAS can be transformed and released from the wastes into leachate and landfill gas. Consequently, it is critical to understand the occurrence and transformation of PFAS in landfills and the effectiveness of landfills, as a disposal alternative, for long-term containment of PFAS. This article presents a state-of-the-art review on the occurrence and transformation of PFAS in landfills, and possible effect of PFAS on the integrity of modern liner systems. Based on the data published from 10 countries (250 + landfills), C4-C7 perfluoroalkyl carboxylic acids were found predominant in the untreated landfill leachate and neutral PFAS, primarily fluorotelomer alcohols, in landfill air. The effectiveness and limitations of the conventional leachate treatment technologies and emerging technologies were also evaluated to address PFAS released into the leachate. Among conventional technologies, reverse osmosis (RO) may achieve a high removal efficiency of 90-100 % based on full-scale data, which, however, is vulnerable to the organic fouling and requires additional disposal of the concentrate. Implications of these knowledge on PFAS management at landfills are discussed and major knowledge gaps are identified.

Metal-doped carbon-supported/modified titanate nanotubes for perfluorooctane sulfonate degradation in water: Effects of preparation conditions, mechanisms, and parameter optimization.

Metal-doped, activated carbon (AC) supported titanate nanotubes (Me/TNTs@AC) have been shown promising for photocatalytic degradation of per- and polyfluoroalkyl substances (PFAS). However, the preparation recipe of the adsorptive photocatalysts has not yet been optimized in terms of type and content of precursor ACs and the metal dopants as well as synthesizing conditions. In this work, the photocatalytic performance of Me/TNTs@AC was evaluated based on the effectiveness in defluorination of pre-sorbed perfluorooctane sulfonic acid (PFOS) after 4-h UV irradiation. Based on the experimental results, the highest photocatalytic mineralization efficiency (66.2 %) of PFOS was achieved using Ga/TNTs@AC prepared under the following conditions: Filtrosorb-400® = 50 wt%, Ga = 2 wt%, hydrothermal treatment temperature = 130 °C, hydrothermal duration = 72 h, and calcination temperature = 550 °C. To understand the underlying mechanisms, selected materials were characterized via X-ray diffraction, the BET surface area and pore volume, UV-vis diffuse reflectance spectrometry, and photoluminescence. The results revealed that the superior photoactivity of Ga/TNTs@AC is attributed to the Ga-facilitated formation of pure crystallized anatase phase during the calcination, high UV light absorption, formation of microscale hybrid AC-anatase-Ga phases, and oxygen defects induced by Ga3+. The information can facilitate preparation and optimization of composite photocatalysts for efficient adsorption and photocatalytic degradation of PFAS in water.

Photocatalytic degradation of GenX in water using a new adsorptive photocatalyst.

GenX, the ammonium salt of hexafluoropropylene oxide dimer acid, has been used as a replacement for perfluorooctanoic acid. Due to its widespread uses, GenX has been detected in waters around the world amid growing concerns about its persistence and adverse health effects. As relevant regulations are rapidly evolving, new technologies are needed to cost-effectively remove and degrade GenX. In this study, we developed an adsorptive photocatalyst by depositing a small amount (3 wt.%) of bismuth (Bi) onto activated-carbon supported titanate nanotubes, Bi/TNTs@AC, and tested the material for adsorption and subsequent solid-phase photodegradation of GenX. Bi/TNTs@AC at 1 g/L was able to adsorb GenX (100 µg/L, pH 7.0) within 1 h, and then degrade 70.0% and mineralize 42.7% of pre-sorbed GenX under UV (254 nm) in 4 h. The efficient degradation also regenerated the material, allowing for repeated uses without chemical regeneration. Material characterizations revealed that the active components of Bi/TNTs@AC included activated carbon, anatase, and Bi nanoparticles with a metallic Bi core and an amorphous Bi2O3 shell. Electron paramagnetic resonance spin-trapping, UV-vis diffuse reflectance spectrometry, and photoluminescence analyses indicated the superior photoactivity of Bi/TNTs@AC was attributed to enhanced light harvesting and generation of charge carriers due to the UV-induced surface plasmon resonance effect, which was enabled by the metallic Bi nanoparticles. •OH radicals and photogenerated holes (h+) were responsible for degradation of GenX. Based on the analysis of degradation byproducts and density functional theory calculations, photocatalytic degradation of GenX started with cleavage of the carboxyl group and/or ether group by •OH, h+, and/or eaq-, and the resulting intermediates were transformed into shorter-chain fluorochemicals following the stepwise defluorination mechanism. Bi/TNTs@AC holds the potential for more cost-effective degradation of GenX and other per- and polyfluorinated alkyl substances.

Concentrate and degrade PFOA with a photo-regenerable composite of In-doped TNTs@AC.

"Concentrate-and-degrade" is an effective strategy to promote mass transfer and degradation of pollutants in photocatalytic systems, yet suitable and cost-effective photocatalysts are required to practice the new concept. In this study, we doped a post-transition metal of Indium (In) on a novel composite adsorptive photocatalyst, activated carbon-supported titanate nanotubes (TNTs@AC), to effectively degrade perfluorooctanoic acid (PFOA). In/TNTs@AC exhibited both excellent PFOA adsorption (>99% in 30 min) and photodegradation (>99% in 4 h) under optimal conditions (25 °C, pH 7, 1 atm, 1 g/L catalyst, 0.1 mg/L PFOA, 254 nm). The heterojunction structure of the composite facilitated a cooperative adsorption mode of PFOA, i.e., binding of the carboxylic head group of PFOA to the metal oxide and attachment of the hydrophobic tail to AC. The resulting side-on adsorption mode facilitates the electron (e‒) transfer from the carboxylic head to the photogenerated hole (h+), which was the major oxidant verified by scavenger tests. Furthermore, the presence of In enables direct electron transfer and facilitates the subsequent stepwise defluorination. Finally, In/TNTs@AC was amenable to repeated uses in four consecutive adsorption-photodegradation runs. The findings showed that adsorptive photocatalysts can be prepared by hybridization of carbon and photoactive semiconductors and the enabled "concentrate-and-degrade" strategy is promising for the removal and degradation of trace levels of PFOA from polluted waters.

H3PO4 activation mediated the iron phase transformation and enhanced the removal of bisphenol A on iron carbide-loaded activated biochar.

Zero valent iron-loaded biochar (Fe0-BC) has shown promise for the removal of various organic pollutants, but is restricted by reduced specific surface area, low utilization efficiency and limited production of reactive oxygen species (ROS). In this study, iron carbide-loaded activated biochar (Fe3C-AB) with a high surface area was synthesized through the pyrolysis of H3PO4 activated biochar with Fe(NO3)3, tested for removing bisphenol A (BPA) and elucidated the adsorption and degradation mechanisms. As a result, H3PO4 activated biochar was beneficial for the transformation of Fe0 to Fe3C. Fe3C-AB exhibited a significantly higher removal rate and removal capacity for BPA than that of Fe0-BC within a wide pH range of 5.0-11.0, and its performance was maintained even under extremely high salinity and different water sources. Moreover, X-ray photoelectron spectra and density functional theory calculations confirmed that hydrogen bonds were formed between the COOH groups and BPA. 1O2 was the major reactive species, constituting 37.0% of the removal efficiency in the degradation of BPA by Fe3C-AB. Density functional reactivity theory showed that degradation pathway 2 of BPA was preferentially attacked by ROS. Thus, Fe3C-AB with low cost and excellent recycling performance could be an alternative candidate for the efficient removal of contaminants.

Mechanochemical destruction and mineralization of solid-phase hexabromocyclododecane assisted by microscale zero-valent aluminum.

Hexabromocyclododecane (HBCD) has been listed in Annex A of the Stockholm Convention as a persistent and bio-accumulative chemical. While HBCD is often present in the solid form for its low solubility, cost-effective technologies have been lacking for the degradation of solid-phase HBCD. In this work, mechanochemical (MC) destruction of high-energy ball milling was employed for direct destruction of solid-phase HBCD, where a strong reducer, microscale zero-valent aluminum (mZVAl), was used as the co-milling agent. The new mZVAl-assisted MC process achieved complete debromination and mineralization of HBCD within 3 h milling. The optimal operating parameters were determined, including the milling atmosphere, the milling speed, the mZVAl-to-HBCD molar ratio, and the ball-to-mZVAl mass ratio. Fourier transform infrared spectrometry and Raman analyses revealed that the organic structures of HBCD were destroyed and organic bromine was completely converted into inorganic bromide, accompanied by the generation of amorphous and graphite carbon. Analysis of the milled samples by GC-MS demonstrated the absence of obvious organic matter after MC treatment, also indicating the complete degradation and conversion of HBCD to inorganic compounds. Further X-ray photoelectron spectroscopic analysis indicates that the fresh surface of mZVAl was generated upon the MC treatment, and Al(0) served as a strong reducing agent (e-donor) for reductive debromination and destruction of the carbon skeleton. The mZVAl-assisted MC milling appears promising as a non-combustion approach for effective destruction and carbonization/mineralization of solid-phase HBCD or potentially other persistent organic pollutants.

FeS-mediated mobilization and immobilization of Cr(III) in oxic aquatic systems.

Reduction of soluble Cr(VI) into insoluble Cr(III) by iron sulfide (FeS) minerals under anoxic conditions has been widely observed in natural and engineered systems. Yet, information has been lacking on the FeS-mediated oxidation and remobilization potential of Cr(III) under varying environmental conditions. The objective of this study was to investigate FeS-mediated redox transformation of Cr(III) to Cr(VI) and the associated mobilization and immobilization when Cr(III)-FeS systems are exposed to atmospheric conditions. The results showed that FeS nanoparticles facilitated rapid and strong Fenton-like reactions during the early-stage oxygenation of FeS, resulting in rapid production of hydroxyl radicals (•OH). Consequently, Cr(III) was rapidly oxidized into Cr(VI). Yet, as the reactions proceeded, the oxidative potential was counteracted by competitive scavenging of •OH by Fe(II) and S(-II) from FeS and the reduction reactions by these electron donors. At equilibrium, all Cr(VI) was reduced back to Cr(III) at an FeS-Cr(III) molar ratio of 10:1, while a small fraction of Cr(VI) persisted in solid products of Cr(OH)3(s) at an FeS-Cr(III) molar ratio of 1:1. Acidic conditions favored the generation of Cr(VI) and the equilibrium concentration of Cr(VI) in oxic FeS NPs systems at pH 5.0 was 1.7 times higher than at pH 9.0. Overall, the FeS-induced Fenton-like reactions and the oxidation of Cr(III) were favored in the early stage, but quenched in the later stage and outcompeted by the reduction of Cr(VI) if sufficient FeS was available. The findings provide new insights into the hydrochemical processes that can affect the speciation, toxicity, and mobility of Cr in aquatic systems containing FeS and Cr.

Heavy metals in agricultural soil in China: A systematic review and meta-analysis.

Research about farmland pollution by heavy metals/metalloids in China has drawn growing attention. However, there was rare information on spatiotemporal evolution and pollution levels of heavy metals in the major grain-producing areas. We extracted and examined data from 276 publications between 2010 and 2021 covering five major grain-producing regions in China from 2010 to 2021. Spatiotemporal evolution characteristics of main heavy metals/metalloids was obtained by meta-analysis. In addition, subgroup analyses were carried out to study preliminary correlations related to accumulation of the pollutants. Cadmium (Cd) was found to be the most prevailing pollutant in the regions in terms of both spatial distribution and temporal accumulation. The Huang-Huai-Hai Plain was the most severely polluted. Accumulation of Cd, mercury (Hg) and copper (Cu) increased from 2010 to 2015 when compared with the 1990 background data. Further, the levels of five key heavy metals (Cd, Cu, Hg, lead [Pb] and zinc [Zn]) showed increasing trends from 2016 to 2021 in all five regions. Soil pH and mean annual precipitation had variable influences on heavy metal accumulation. Alkaline soil and areas with less rainfall faced higher pollution levels. Farmlands cropped with mixed species showed smaller effect sizes of heavy metals than those with single upland crop, suggesting that mixed farmland use patterns could alleviate the levels of heavy metals in soil. Of various soil remediation efforts, farmland projects only held a small market share. The findings are important to support the research of risk assessment, regulatory development, pollution prevention, fund allocation and remediation actions.

Field demonstration of on-site immobilization of arsenic and lead in soil using a ternary amending agent.

Soil contamination by heavy metals and metalloids has been a major environmental challenge. While various remediation technologies have been reported, field data on the remediation effectiveness have been limited. We tested a new remediation technology for on-site immobilization of As(III) and Pb(II) in a contaminated soil at an abandoned chemical plant site. A novel ternary amending agent consisting of Fe2O3, MnO2, and Mg(OH)2 (molar ratio = 1.0:5.5:5.5) was used to amend the soil on-site. Field monitoring data indicated that the amendment severed as a pH buffer and a long-term sequester for both As and Pb in the soil. At a dosage of 3 wt%, the acid-leachable As and Pb were lowered from 0.042-0.077 mg/L and 0.013-0.022 mg/L to 0.0062-0.0093 mg/L and 0.0030-0.0080 mg/L, respectively, after one day of the amendment, and to 0.0020-0.0050 mg/L and 0.0020-0.0054 mg/L after 240 days of aging. As(III) was oxidized to As(V) and subsequently immobilized via complexation and precipitation, whereas Pb(II) was sequestered via electrostatic attraction and chemical precipitation. The treatment cost was estimated at $31.5/m3. The results indicate that complex contaminants in soil can be effectively immobilized using combined amending agents that can interact with the target chemicals and induce synergistic immobilization reactions.

Aggregation of carboxyl-modified polystyrene nanoplastics in water with aluminum chloride: Structural characterization and theoretical calculation.

Nanoplastics (NPs) pollution of aquatic systems is becoming an emerging environmental issue due to their stable structure, high mobility, and easy interactions with ambient contaminants. Effective removal technologies are urgently needed to mitigate their toxic effects. In this study, we systematically investigated the removal effectiveness and mechanisms of a commonly detected nanoplastics, carboxyl-modified polystyrene (PS-COOH) via coagulation and sedimentation processes using aluminum chloride (AlCl3) as a coagulant. PS-COOH appeared as clearly defined and discrete spherical nanoparticles in water with a hydrodynamic diameter of 50 nm. The addition of 10 mg/L AlCl3 compressed and even destroyed the negatively charged PS-COOH surface layer, decreased the energy barrier, and efficiently removed 96.6% of 50 mg/L PS-COOH. The dominant removal mechanisms included electrostatic adsorption and intermolecular interactions. Increasing the pH from 3.5 to 8.5 sharply enhanced the PS-COOH removal, whereas significant loss was observed at pH 10.0. High temperature (23 °C) favored the removal of PS-COOH compared to lower temperature (4 °C). High PS-COOH removal efficiency was observed over the salinity range of 0 - 35‰. The presence of positively charged Al2O3 did not affect the PS-COOH removal, while negatively charged SiO2 reduced the PS-COOH removal from 96.6% to 93.2%. Moreover, the coagulation and sedimentation process efficiently removed 90.2% of 50 mg/L PS-COOH in real surface water even though it was rich in inorganic ions and total organic carbon. The fast and efficient capture of PS-COOH by AlCl3 via a simple coagulation and sedimentation process provides a new insight for the treatment of NPs from aqueous environment.

Learning Cognitive Map Representations for Navigation by Sensory-Motor Integration.

How to transform a mixed flow of sensory and motor information into memory state of self-location and to build map representations of the environment are central questions in the navigation research. Studies in neuroscience have shown that place cells in the hippocampus of the rodent brains form dynamic cognitive representations of locations in the environment. We propose a neural-network model called sensory-motor integration network model (SeMINet) to learn cognitive map representations by integrating sensory and motor information while an agent is exploring a virtual environment. This biologically inspired model consists of a deep neural network representing visual features of the environment, a recurrent network of place units encoding spatial information by sensorimotor integration, and a secondary network to decode the locations of the agent from spatial representations. The recurrent connections between the place units sustain an activity bump in the network without the need of sensory inputs, and the asymmetry in the connections propagates the activity bump in the network, forming a dynamic memory state which matches the motion of the agent. A competitive learning process establishes the association between the sensory representations and the memory state of the place units, and is able to correct the cumulative path-integration errors. The simulation results demonstrate that the network forms neural codes that convey location information of the agent independent of its head direction. The decoding network reliably predicts the location even when the movement is subject to noise. The proposed SeMINet thus provides a brain-inspired neural-network model for cognitive map updated by both self-motion cues and visual cues.

A 'Concentrate-&-Destroy' technology for enhanced removal and destruction of per- and polyfluoroalkyl substances in municipal landfill leachate.

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in landfill leachate due to their widespread applications in various industrial and consumer products. Yet, there has been no cost-effective technology available for treating PFAS in leachate because of the intrinsic persistency of PFAS and the high matrix strength of landfill leachate. We tested a two-step 'Concentrate-&-Destroy' technology for treating over 14 PFAS from a model landfill leachate through bench- and pilot-scale experiments. The technology was based on an adsorptive photocatalyst (Fe/TNTs@AC), which was able to selectively adsorb PFAS despite the strong matrix effect of the leachate. Moreover, the pre-concentrated PFAS on Fe/TNTs@AC were effectively degraded under UV, which also regenerates the material. The presence of 0.5 M H2O2 during the photocatalytic degradation enhanced the solid-phase destruction of the PFAS. Fresh Fe/TNTs@AC at a dosage of 10 g/L removed >95% of 13 PFAS from the leachate, 86% after first regeneration, and 74% when reused three times. Fe/TNTs@AC was less effective for PFBA and PFPeA partially due to the transformation of precursors and/or longer-chain homologues into these short-chain PFAS. Pilot-scale tests preliminarily confirmed the bench-scale results. Despite the strong interference from additional suspended solids, Fe/TNTs@AC removed >92% of 18 PFAS in 8 h under the field conditions, and when the PFAS-laden solids were subjected to the UV-H2O2 system, ~84% of 16 PFAS in the solid phase were degraded. The 'Concentrate-&-Destroy' strategy appears promising for more cost-effective removal and degradation of PFAS in landfill leachate or PFAS-laden high-strength wastewaters.