Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

Hexavalent chromium in drinking water: Chemistry,challenges and future outlook on Sn(II)- and photocatalyst-based treatment

• Wide occurrence of Cr(VI) in US source drinking water. • A strong dependence of occurrence on groundwater sources. • Elucidate Redox and equilibrium chemistry of Cr(VI). • Sn(II)-based and TiO₂-based reductive treatments hold extreme promise. • Key challenges include residual waste, Cr(VI) re-generation and socioeconomic drivers. Chromium (Cr) typically exists in either trivalent and hexavalent oxidation states in drinking water, i.e., Cr(III) and Cr(VI), with Cr(VI) of particular concern in recent years due to its high toxicity and new regulatory standards. This Account presented a critical analysis of the sources and occurrence of Cr(VI) in drinking water in the United States, analyzed the equilibrium chemistry of Cr(VI) species, summarized important redox reaction relevant to the fate of Cr(VI) in drinking water, and critically reviewed emerging Cr(VI) treatment technologies. There is a wide occurrence of Cr(VI) in US source drinking water, with a strong dependence on groundwater sources, mainly due to naturally weathering of chromium-containing aquifers. Challenges regarding traditional Cr(VI) treatment include chemical cost, generation of secondary waste and inadvertent re-generation of Cr(VI) after treatment. To overcome these challenges, reductive Cr(VI) treatment technologies based on the application of stannous tin or electron-releasing titanium dioxide photocatalyst hold extreme promise in the future. To moving forward in the right direction, three key questions need further exploration for the technology implementation, including effective management of residual waste, minimizing the risks of Cr(VI) re-occurrence downstream of drinking water treatment plant, and promote the socioeconomic drivers for Cr(VI) control in the future.     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

Long-term adaptive evolution of Shewanella oneidensis MR-1 for establishment of high concentration Cr(VI) tolerance

• Shewanella oneidensis MR-1 was acclimated to grow with Cr(VI) of 190 mg/L. • Whole genomes from 7 populations at different acclimation stages were sequenced. • Gene mutations mainly related to efflux pumps and transporters. • An adaptation mechanism of MR-1 to high concentration of Cr(VI) was proposed. Acclimation is the main method to enhance the productivity of microorganisms in environmental biotechnology, but it remains uncertain how microorganisms acquire resistance to high concentrations of pollutants during long-term acclimation. Shewanella oneidensis MR-1 was acclimated for 120 days with increasing hexavalent chromium (Cr(VI)) concentrations from 10 to 190 mg/L. The bacterium was able to survive from the highly toxic Cr(VI) environment due to its enhanced capability to reduce Cr(VI) and the increased cell membrane surface. We sequenced 19 complete genomes from 7 populations of MR-1, including the ancestral strain, the evolved strains in Cr(VI) environment on days 40, 80 and 120 and their corresponding controls. A total of 27, 49 and 90 single nucleotide polymorphisms were found in the Cr(VI)-evolved populations on days 40, 80 and 120, respectively. Nonsynonymous substitutions were clustered according to gene functions, and the gene mutations related to integral components of the membrane, including efflux pumps and transporters, were the key determinants of chromate resistance. In addition, MR-1 strengthened the detoxification of Cr(VI) through gene variations involved in adenosine triphosphate binding, electron carrier activity, signal transduction and DNA repair. Our results provide an in-depth analysis of how Cr(VI) resistance of S. oneidensis MR-1 is improved by acclimation, as well as a genetic understanding of the impact of long-term exposure of microorganisms to pollution.     

Review on remediation technologies for arsenic-contaminated soil

• Recent progress of As-contaminated soil remediation technologies is presented. • Phytoextraction and chemical immobilization are the most widely used methods. • Novel remediation technologies for As-contaminated soil are still urgently needed. • Methods for evaluating soil remediation efficiency are lacking. • Future research directions for As-contaminated soil remediation are proposed. Arsenic (As) is a top human carcinogen widely distributed in the environment. As-contaminated soil exists worldwide and poses a threat on human health through water/food consumption, inhalation, or skin contact. More than 200 million people are exposed to excessive As concentration through direct or indirect exposure to contaminated soil. Therefore, affordable and efficient technologies that control risks caused by excess As in soil must be developed. The presently available methods can be classified as chemical, physical, and biological. Combined utilization of multiple technologies is also common to improve remediation efficiency. This review presents the research progress on different remediation technologies for As-contaminated soil. For chemical methods, common soil washing or immobilization agents were summarized. Physical technologies were mainly discussed from the field scale. Phytoextraction, the most widely used technology for As-contaminated soil in China, was the main focus for bioremediation. Method development for evaluating soil remediation efficiency was also summarized. Further research directions were proposed based on literature analysis.     

Fabrication of highly efficient Bi2WO6/CuS composite for visible-light photocatalytic removal of organic pollutants and Cr(VI) from wastewater

• A novel Bi₂WO₆/CuS composite was fabricated by a facile solvothermal method. • This composite efficiently removed organic pollutants and Cr(VI) by photocatalysis. • The DOM could promoted synchronous removal of organic pollutants and Cr(VI). • This composite could be applied at a wide pH range in photocatalytic reactions. • Possible photocatalytic mechanisms of organic pollutants and Cr(VI) were proposed. A visible-light-driven Bi₂WO₆/CuS p-n heterojunction was fabricated using an easy solvothermal method. The Bi₂WO₆/CuS exhibited high photocatalytic activity in a mixed system containing rhodamine B (RhB), tetracycline hydrochloride (TCH), and Cr (VI) under natural conditions. Approximately 98.8% of the RhB (10 mg/L), 87.6% of the TCH (10 mg/L) and 95.1% of the Cr(VI) (15 mg/L) were simultaneously removed from a mixed solution within 105 min. The removal efficiencies of TCH and Cr(VI) increased by 12.9% and 20.4%, respectively, in the mixed solution, compared with the single solutions. This is mainly ascribed to the simultaneous consumption electrons and holes, which increases the amount of excited electrons/holes and enhances the separation efficiency of photogenerated electrons and holes. Bi₂WO₆/CuS can be applied over a wide pH range (2–6) with strong photocatalytic activity for RhB, TCH and Cr(VI). Coexisiting dissolved organic matter in the solution significantly promoted the removal of TCH (from 74.7% to 87.2%) and Cr(VI) (from 75.7% to 99.9%) because it accelerated the separation of electrons and holes by consuming holes as an electron acceptor. Removal mechanisms of RhB, TCH, and Cr(VI) were proposed, Bi₂WO₆/CuS was formed into a p-n heterojunction to efficiently separate and transfer photoelectrons and holes so as to drive photocatalytic reactions. Specifically, when reducing pollutants (e.g., TCH) and oxidizing pollutants (e.g., Cr(VI)) coexist in wastewater, the p-n heterojunction in Bi₂WO₆/CuS acts as a “bridge” to shorten the electron transport and thus simultaneously increase the removal efficiencies of both types of pollutants.     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized. • The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K. • The potential mechanism for Cr(VI) adsorption by NHPC was put forward. • DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI). To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).     

In situ synthesis of FeS/Carbon fibers for the effective removal of Cr(VI) in aqueous solution

• FeS/carbon fibers were in situ synthesized with Fe-carrageenan hydrogel fiber. • The double helix structure of carrageenan is used to load and disperse Fe. • Pyrolyzing sulfate groups enriched carrageenan-Fe could easily generate FeS. • The adsorption mechanisms include reduction and complexation reaction. Iron sulfide (FeS) nanoparticles (termed FSNs) have attracted much attention for the removal of pollutants due to their high efficiency and low cost, and because they are environmentally friendly. However, issues of agglomeration, transformation, and the loss of active components limit their application. Therefore, this study investigates in situ synthesized FeS/carbon fibers with an Fe-carrageenan biomass as a precursor and nontoxic sulfur source to ascertain the removal efficiency of the fibers. The enrichment of sulfate groups as well as the double-helix structure in ι-carrageenan-Fe could effectively avoid the aggregation and loss of FSNs in practical applications. The obtained FeS/carbon fibers were used to control a Cr(VI) polluted solution, and exhibited a relatively high removal capacity (81.62 mg/g). The main mechanisms included the reduction of FeS, electrostatic adsorption of carbon fibers, and Cr(III)-Fe(III) complexation reaction. The pseudo-second-order kinetic model and Langmuir adsorption model both provided a good fit of the reaction process; hence, the removal process was mainly controlled by chemical adsorption, specifically monolayer adsorption on a uniform surface. Furthermore, co-existing anions, column, and regeneration experiments indicated that the FeS/carbon fibers are a promising remediation material for practical application.     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

A “Seawater-in-Sludge” approach for capacitive biochar production via the alkaline and alkaline earth metals activation

• Capacitive biochar was produced from sewage sludge. • Seawater was proved to be an alternative activation agent. • Minerals vaporization increased the surface area of biochar. • Molten salts acted as natural templates for the development of porous structure. Sewage sludge is a potential precursor for biochar production, but its effective utilization involves costly activation steps. To modify biochar properties while ensuring cost-effectiveness, we examined the feasibility of using seawater as an agent to activate biochar produced from sewage sludge. In our proof-of-concept study, seawater was proven to be an effective activation agent for biochar production, achieving a surface area of 480.3 m²/g with hierarchical porosity distribution. Benefited from our design, the catalytic effect of seawater increased not only the surface area but also the graphitization degree of biochar when comparing the pyrolysis of sewage sludge without seawater. This leads to seawater activated biochar electrodes with lower resistance, higher capacitance of 113.9 F/g comparing with control groups without seawater. Leveraging the global increase in the salinity of groundwater, especially in coastal areas, these findings provide an opportunity for recovering a valuable carbon resource from sludge.     

Stabilization of hexavalent chromium with pretreatment and high temperature sintering in highly contaminated soil

• Separate reduction and sintering cannot be effective for Cr stabilization. • Combined treatment of reduction and sintering is effective for Cr stabilization. • Almost all the Cr in the reduced soil is residual form after sintering at 1000°C. This study explored the effectiveness and mechanisms of high temperature sintering following pre-reduction with ferric sulfate (FeSO₄), sodium sulfide (Na₂S), or citric acid (C₆H₈O₇) in stabilizing hexavalent chromium (Cr(VI)) in highly contaminated soil. The soil samples had an initial total Cr leaching of 1768.83 mg/L, and Cr(VI) leaching of 1745.13 mg/L. When FeSO₄ or C₆H₈O₇ reduction was followed by sintering at 1000°C, the Cr leaching was reduced enough to meet the Safety Landfill Standards regarding general industrial solid waste. This combined treatment greatly improved the stabilization efficiency of chromium because the reduction of Cr(VI) into Cr(III) decreased the mobility of chromium and made it more easily encapsulated in minerals during sintering. SEM, XRD, TG-DSC, and speciation analysis indicated that when the sintering temperature reached 1000°C, almost all the chromium in soils that had the pre-reduction treatment was transformed into the residual form. At 1000°C, the soil melted and promoted the mineralization of Cr and the formation of new Cr-containing compounds, which significantly decreased subsequent leaching of chromium from the soil. However, without reduction treatment, chromium continued to leach from the soil even after being sintered at 1000°C, possibly because the soil did not fully fuse and because Cr(VI) does not bind with soil as easily as Cr(III).     

Synthesis of vinasse-dolomite nanocomposite biochar via a novel developed functionalization method to recover phosphate as a potential fertilizer substitute

• Nanocomposites were prepared by adding dolomite to vinasse at different ratio. • Textural and morphological features of adsorbents were studied in detail. • CCD based RSM was used for investigation of P ion removal by nanocomposite. • The q_m based on Langmuir model for modified vinasse biochar was 178.57 mg/g. • P loaded nanocomposite improved plant growth and could be utilized as P-fertilizer. The effectiveness of phosphate (P) removal from aqueous solutions was investigated by novel low-cost biochars synthesized from vinasse and functionalized with calcined dolomite. The vinasse-derived biochar, synthesized via pyrolysis at different temperatures, showed easy preparation and a large surface area. The novel vinasse biochar nanocomposites were prepared by adding dolomite to the vinasse biochars with different weight percentages (10, 20 and 30%). The characteristics of the prepared materials were identified for further understanding of the inherent adsorption mechanism between P ions and vinasse biochars. Vinasse-dolomite nanocomposite was very effective in the adsorption of P species from aqueous media. The effect of the operational factors on Vinasse-dolomite nanocomposite was explored by applying response surface methodology (RSM). According to RSM results, the optimum condition was achieved to be contact time 90 (min), 250 (mg/L) of P concentration and pH 7. Thermodynamic isotherm and kinetic studies were applied on experimental data to understand the adsorption behavior. The Vinasse-dolomite nanocomposite revealed preferential P species adsorption in the presence of co-existing anions. The P species could be recovered by 1.0 M HCl where the efficiency was not affected up to the fifth cycle. The P-loaded Vinasse-dolomite nanocomposite was successfully tested on a plant; it significantly improved its growth and proved its potency as a P-based fertilizer substitute.     

Adsorption characteristics of ciprofloxacin onto g-MoS2 coated biochar nanocomposites

• The g-MoS₂ coated composites (g-MoS₂-BC) were synthesized. • The coated g-MoS₂ greatly increased the adsorption ability of biochar. • The synergistic effect was observed for CIP adsorption on g-MoS₂-RC700. • The adsorption mechanisms of CIP on g-MoS₂-BC were proposed. The g-MoS₂ coated biochar (g-MoS₂-BC) composites were synthesized by coating original biochar with g-MoS₂ nanosheets at 300°C(BC300)/700°C (BC700). The adsorption properties of the g-MoS₂-BC composites for ciprofloxacin (CIP) were investigated with an aim to exploit its high efficiency toward soil amendment. The specific surface area and the pore structures of biochar coated g-MoS₂ nanosheets were significantly increased. The g-MoS₂-BC composites provided more π electrons, which was favorable in enhancing the π-π electron donor-acceptor (EDA) interactions between CIP and biochar. As a result, the g-MoS₂-BC composites showed faster adsorption rate and greater adsorption capacity for CIP than the original biochar. The coated g-MoS₂ nanosheets contributed more to CIP adsorption on the g-MoS₂-BC composites due to their greater CIP adsorption capacity than the original biochar. Moreover, the synergistic effect was observed for CIP adsorption on g-MoS₂-BC700, and suppression effect on g-MoS₂-BC300. In addition, the adsorption of CIP onto g-MoS₂-BC composites also exhibited strong dependence on the solution pH, since it can affect both the adsorbent surface charge and the speciation of contaminants. It was reasonably suggested that the mechanisms of CIP adsorption on g-MoS₂-BC composites involved pore-filling effects, π-π EDA interaction, electrostatic interaction, and ion exchange interaction. These results are useful for the modification of biochar in exploiting the novel amendment for contaminated soils.     

Sorption of aromatic organophosphate flame retardants on thermally and hydrothermally produced biochars

• TPhP showed faster and higher sorption on biochars than TPPO. • Pyrochars had higher sorption capacity for TPPO than hydrochar. • Hydrophobic interactions dominated TPhP sorption by biochars. • The π-π EDA and electrostatic interactions are involved in sorption. Aromatic organophosphate flame retardant (OPFR) pollutants and biochars are commonly present and continually released into soils due to their increasingly wide applications. In this study, for the first time, the sorption of OPFRs on biochars was investigated. Although triphenyl phosphate (TPhP) and triphenylphosphine oxide (TPPO) have similar molecular structures and sizes, TPhP exhibited much faster and higher sorption than TPPO due to its stronger hydrophobicity, suggesting the dominant role of hydrophobic interactions in TPhP sorption. The π-π electron donor–acceptor (EDA) interactions also contributed to the sorption process, as suggested by the negative correlation between the sorption capacity of the aromatic OPFRs and the aromatic index (H/C atomic ratios) of biochar. Density functional theory calculations further showed that one benzene ring of aromatic OPFRs has no electrons, which may interact with biochar via π-π EDA interactions. The electrostatic attraction between the protonated P = O in OPFRs and the negatively charged biochar was found to occur at pH below 7. This work provides insights into the sorption behaviors and mechanisms of aromatic OPFRs by biochars.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Remediation of soil and groundwater contaminated with organic chemicals using stabilized nanoparticles: Lessons from the past two decades

▪ Overviewed evolution and environmental applications of stabilized nanoparticles. ▪ Reviewed theories on particle stabilization for enhanced reactivity/deliverability. ▪ Examined various in situ remediation technologies based on stabilized nanoparticles. ▪ Summarized knowledge on transport of stabilized nanoparticles in porous media. ▪ Identified key knowledge gaps and future research needs on stabilized nanoparticles. Due to improved soil deliverability and high reactivity, stabilized nanoparticles have been studied for nearly two decades for in situ remediation of soil and groundwater contaminated with organic pollutants. While large amounts of bench- and field-scale experimental data have demonstrated the potential of the innovative technology, extensive research results have also unveiled various merits and constraints associated different soil characteristics, types of nanoparticles and particle stabilization techniques. Overall, this work aims to critically overview the fundamental principles on particle stabilization, and the evolution and some recent developments of stabilized nanoparticles for degradation of organic contaminants in soil and groundwater. The specific objectives are to: 1) overview fundamental mechanisms in nanoparticle stabilization; 2) summarize key applications of stabilized nanoparticles for in situ remediation of soil and groundwater contaminated by legacy and emerging organic chemicals; 3) update the latest knowledge on the transport and fate of stabilized nanoparticles; 4) examine the merits and constraints of stabilized nanoparticles in environmental remediation applications; and 5) identify the knowledge gaps and future research needs pertaining to stabilized nanoparticles for remediation of contaminated soil and groundwater. Per instructions of this invited special issue, this review is focused on contributions from our group (one of the pioneers in the subject field), which, however, is supplemented by important relevant works by others. The knowledge gained is expected to further advance the science and technology in the environmental applications of stabilized nanoparticles.     

Chromium phytoextraction and physiological responses of the hyperaccumulator Leersia hexandra Swartz to plant growth-promoting rhizobacterium inoculation

● Improved Cr phytoextration efficiency was achieved by B. cereus inoculation. ● B. cereus could produce plant-beneficial PGPR factors at diverse Cr stresses. ● Enhanced resistance of inoculated L. hexandra towards elevated Cr stress. ● The majority of Cr existed in the stable forms in the tissues of L. hexandra. Phytoextraction is a promising option for purifying hexavalent chromium (Cr(VI))-laden wastewater, but the long remediation period incurred by poor growth rate of Cr hyperaccumulators remains a primary hindrance to its large-scale application. In this study, we performed a hydroponic experiment to evaluate the feasibility of promoting the growth and phytoextraction efficiency of Cr hyperaccumulator Leersia hexandra Swartz (L. hexandra) by inoculating plant growth-promoting rhizobacteria (PGPR) Bacillus cereus (B. cereus). In batch tests, the Cr(VI) removal rates of L. hexandra and B. cereus co-culture were greater than the sum of their respective monocultures. This was likely due to the microbial reduction of Cr(VI) to Cr(III), which is amiable to plant uptake. Besides, the PGPR factors of B. cereus, including indoleacetic acid (IAA) production, 1-aminocyclopropane-1-carboxylic acid deamination (ACCd) activity, phosphate solubilization capacity, and siderophore production, were quantified. These PGPR factors helped explain the biomass augmentation, root elongation and enhanced Cr enrichment of the inoculated L. hexandra in pot experiments. Despite the increased Cr uptake, no aggravated oxidative damage to the cell membrane was observed in the inoculated L. hexandra. This was attributed to its capacity to confront the increased intracellular Cr stress by upregulating both the activities of antioxidative enzymes and expression of metal-binding proteins/peptides. Moreover, L. hexandra could always conserve the majority of Cr in the residual and oxalic integrated forms with low mobility and phytotoxicity, irrespective of the B. cereus inoculation. These results highlight the constructed Cr hyperaccumulator-rhizobacteria consortia as an effective candidate for decontaminating Cr(VI)-laden wastewater.     

Dual-functional sites for synergistic adsorption of Cr(VI) and Sb(V) by polyaniline-TiO2 hydrate: Adsorption behaviors,sites and mechanisms

• PANI/Ti(OH)_n^(4–n)+ exhibited excellent adsorption capacity and reusability. • Adsorption sites of Cr(VI) were hydroxyl, amino/imino group and benzene rings. • Sb(V) was adsorbed mainly through hydrogen bonds and Ti-O-Sb. • The formation of Cr-O-Sb in dual system demonstrated the synergistic adsorption. • PANI/TiO₂ was a potential widely-applied adsorbent and worth further exploring. Removal of chromium (Cr) and antimony (Sb) from aquatic environments is crucial due to their bioaccumulation, high mobility and strong toxicity. In this work, a composite adsorbent consisting of Ti(OH)_n^(4–n)+ and polyaniline (PANI) was designed and successfully synthesized by a simple and eco-friendly method for the uptake of Cr(VI) and Sb(V). The synthetic PANI/TiO₂ composites exhibited excellent adsorption capacities for Cr(VI) and Sb(V) (394.43 mg/g for Cr(VI) and 48.54 mg/g for Sb(V)), wide pH applicability and remarkable reusability. The adsorption of Cr(VI) oxyanions mainly involved electrostatic attraction, hydrogen bonding and anion-π interactions. Based on X-ray photoelectron spectroscopy and FT-IR analysis, the adsorption sites were shown to be hydroxyl groups, amino/imino groups and benzene rings. Sb(V) was adsorbed mainly through hydrogen bonds and surface complexation to form Ti-O-Sb complexes. The formation of Cr-O-Sb in the dual system demonstrated the synergistic adsorption of Cr(VI) and Sb(V). More importantly, because of the different adsorption sites, the adsorption of Cr(VI) and Sb(V) occurred independently and was enhanced to some extent in the dual system. The results suggested that PANI/TiO₂ is a promising prospect for practical wastewater treatment in the removal of Cr(VI) and Sb(V) from wastewater owing to its availability, wide applicability and great reusability.     

Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars

• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%. Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K⁺ and NH₄⁺. Phosphorus adsorption was related to oxidation and interaction between PO₄^3– and Fe³⁺. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.