Fabrication of cobalt-iron Prussian blue analogues functionalized hybrid membranes for efficiently capturing Tl from water: Performance and mechanism.

As trace levels of thallium (Tl) in water are lethal to humans and ecosystems, it is essential to exploit advanced technologies for efficient Tl removal. In response to this concern, an innovative composite membrane was developed, incorporating polytetrafluoroethylene (PTFE) and featuring a dual-support system with polydopamine (PDA) and polyethyleneimine (PEI), along with bimetallic Prussian blue analogues (Co@Fe-PBAs) as co-supports. The composite membrane exhibited an exceptional Tl+-adsorption capacity (qm) of 186.1 mg g-1 when utilized for the treatment of water containing low concentration of Tl+ (0.5 mg⋅L-1). Transmission electron microscopy displayed the obvious Tl+ mapping inside the special hollow Co@Fe-PBAs crystals, demonstrating the deep intercalation of Tl+ via ion exchange and diffusion. The Tl+-adsorption capability of the composite membrane was not greatly affected by coexisting Na+, Ca2+ and Mg2+ as well as the tricky K+, indicating the excellent anti-interference. Co-doped PBAs enhanced ion exchange and intercalation of the composite membrane with Tl+ leading to excellent Tl+ removal efficiency. The composite membrane could efficiently remove Tl+ from thallium-contaminated river water to meet the USEPA standard. This study provides a cost-effective membrane-based solution for efficient Tl+ removal from Tl+-containing wastewater.

Comprehensive strategies for microcystin degradation: A review of the physical, chemical, and biological methods and genetic engineering.

Addressing the threat of harmful cyanobacterial blooms (CyanoHABs) and their associated microcystins (MCs) is crucial for global drinking water safety. In this review, we comprehensively analyze and compares the physical, chemical, and biological methods and genetic engineering for MCs degradation in aquatic environments. Physical methods, such as UV treatments and photocatalytic reactions, have a high efficiency in breaking down MCs, with the potential for further enhancement in performance and reduction of hazardous byproducts. Chemical treatments using chlorine dioxide and potassium permanganate can reduce MC levels but require careful dosage management to avoid toxic by-products and protect aquatic ecosystems. Biological methods, including microbial degradation and phytoremediation techniques, show promise for the biodegradation of MCs, offering reduced environmental impact and increased sustainability. Genetic engineering, such as immobilization of microcystinase A (MlrA) in Escherichia coli and its expression in Synechocystis sp., has proven effective in decomposing MCs such as MC-LR. However, challenges related to specific environmental conditions such as temperature variations, pH levels, presence of other contaminants, nutrient availability, oxygen levels, and light exposure, as well as scalability of biological systems, necessitate further exploration. We provide a comprehensive evaluation of MCs degradation techniques, delving into their practicality, assessing the environmental impacts, and scrutinizing their efficiency to offer crucial insights into the multifaceted nature of these methods in various environmental contexts. The integration of various methodologies to enhance degradation efficiency is vital in the field of water safety, underscoring the need for ongoing innovation.

Enhanced removal of trace thallium by photo-promoted adsorption using Prussian blue@filter papers: Performance and mechanistic insights.

Developing highly efficient adsorbents for the removal of trace thallium(I) (Tl+) is crucial for addressing environmental challenges. In this study, we successfully synthesized cubic Prussian blue (PB) loading on filter papers using an intermediate layer (dopamine/polyethyleneimine) via in-situ methods. The as-prepared PB-modified FP demonstrated outstanding anti-interference properties and light-enhanced adsorption performance for Tl+ (0.5 mg/L) under ultraviolet (UV) irradiation, exhibiting twice the effectiveness compared to dark conditions, even in acidic and coexisting ionic environments. This indicated its suitability for treating complex Tl+-contaminated water. Notably, the removal efficiency for trace Tl+ was almost 100%, with a maximum experimental adsorption capacity of 86.2 mg/g after 1-h photo-promoted adsorption under 365 nm UV. Characterization results supported a proposed photo-driven redox mechanism that elucidated the interaction between Tl+ and PB-modified FP. Specifically, the accelerated Fe(III) to Fe(II) redox reaction facilitated Tl+ accommodation on the surface and/or lattice of PB, enhancing Tl+ adsorption by compensating for missed positive charges. This study provides valuable insights into utilizing PB-based materials to enhance the photo-enhanced Tl+ adsorption capacity in a cost-effective, easy-to-synthesize, and environmentally friendly manner.

Remediation of arsenic-contaminated soil using nanoscale schwertmannite synthesized by persulfate oxidation with carboxymethyl cellulose stabilization.

Schwertmannite (SCH) is a promising material for adsorbing inorganic arsenic (As). We synthesized SCH nanoparticles (nano-SCH) via a modified chemical oxidation method and investigated the application of nano-SCH for the remediation of As-contaminated soils. The production of nano-SCH was successfully prepared using the persulfate oxidation method with carboxymethyl cellulose stabilization. The spherical structure of the nano-SCH particles had an average hydrodynamic diameter of 296 nm with high specific surface areas (108.9 m2/g). Compared with SCH synthesized via the H2O2 oxidation method, the percentage of Fe3+ precipitation in nano-SCH synthesis increased from 63.2% to 84.1%. The inorganic As adsorption capacity of nano-SCH improved by 2.27 times at solution pH = 6. After remediation of heavily As-contaminated soils by using 5% nano-SCH, the leachability of inorganic As rapidly decreased to 0.01% in 30 d. Correspondingly, the immobilization efficiencies of inorganic As in soil reached >99.9%. The inorganic As fractions in treated soil shifted from specifically and nonspecifically bound forms to amorphous and crystalline hydrous oxide-bound fractions. After treatment with 5% nano-SCH for 60 d, soil pH slightly decreased from 5.47 to 4.94; by contrast, soil organic matter content increased by 20.9%. Simultaneously, dehydrogenase concentration in soil decreased by 22.4%-34.7% during the remediation process. These changes in soil properties and As immobilization jointly decreased microbial activity and initiated the re-establishment of bacterial communities in the soil. In summary, this study presents a novel and high-productivity technology for nano-SCH synthesis and confirms the high As immobilization effectiveness of nano-SCH in the remediation of As-contaminated soils.

Reduction and adsorption of uranium(VI) from aqueous solutions using nanoscale zero-valent manganese.

Nano zero-valent manganese (nZVMn) is theoretically expected to exhibit high reducibility and adsorption capacity, yet its feasibility, performance, and mechanism for reducing and adsorbing hexavalent uranium (U(VI)) from wastewater remain unclear. In this study, nZVMn was prepared via borohydride reduction, and its behaviors about reduction and adsorption of U(VI), as well as the underlying mechanism, were investigated. Results indicated that nZVMn exhibited a maximum U(VI) adsorption capacity of 625.3 mg/g at a pH of 6 and an adsorbent dosage of 1 g/L, and the co-existing ions (K+, Na+, Mg2+, Cd2+, Pb2+, Tl+, Cl-) at studied range had little interference on U(VI) adsorption. Furthermore, nZVMn effectively removed U(VI) from rare-earth ore leachate at a dosage of 1.5 g/L, resulting in a U(VI) concentration of lower than 0.017 mg/L in the effluent. Comparative tests demonstrated the superiority of nZVMn over other manganese oxides (Mn2O3 and Mn3O4). Characterization analyses, including X-ray diffraction and depth profiling X-ray photoelectron spectroscopy, combined with density functional theory calculation revealed that the reaction mechanism of U(VI) using nZVMn involved reduction, surface complexation, hydrolysis precipitation, and electrostatic attraction. This study provides a new alternative for efficient removal of U(VI) from wastewater and improves the understanding of the interaction between nZVMn and U(VI).

Thallium removal from wastewater using sulfidized zero-valent manganese: Effects of sulfidation method and liquid nitrogen pretreatment.

Zero-valent manganese (ZVMn) possesses high reducibility in theory, while sulfide exhibits strong affinity towards a variety of heavy metals owing to the low solubility of metal sulfides. Yet the performance and mechanisms on using sulfidized zero-valent manganese (SZVMn) to remove thallium (Tl) from wastewater still remain unclear. In this study, the performance of Tl(I) removal using SZVMn synthesized by borohydrides reduction followed by sulfides modification, with and without liquid nitrogen treatment, was compared and the mechanism behind was investigated. The results show that at a S/Mn molar ratio of 1.0, liquid nitrogen modified SZVMn (LSZVMn) possessed more interior channels and pores than SZVMn, with 65.3% higher specific surface area and 73.7% higher porosity, leading to 6.4-8.1% improvement in adsorption of Tl(I) at pH 4-10. LSZVMn showed effectiveness and robustness in Tl(I) removal in the presence of co-existing ions up to 0.1 M. The adsorption of Tl(I) conformed to the pseudo-1st-order kinetic model, and followed the Langmuir isothermal model, with the maximum Tl adsorption capacity of 264.9 mg·g-1 at 288 K. The mechanism of Tl(I) removal with SZVMn was found to include sulfidation-induced precipitation, manganese reduction, surface complexation, and electrostatic attraction. The liquid nitrogen pretreatment embrittled and cracked the outer shell of S/Mn compounds, resulted in a highly hierarchical structure, enhancing the manganese reduction and improving the Tl(I) removal. Based on the above results, the SZVMn and its liquid nitrogen-modified derivatives are novel and effective environmental materials for Tl(I) removal from wastewater, and the application of SZVMn to the removal of other pollutants merits investigation in future study.

Efficient removal of antimonate and antimonite by a novel lanthanum-manganese binary oxide: Performance and mechanism.

Antimony is a highly toxic pollutant and its removal from water gains increasing attention. To effectively remove both Sb(III) and Sb(V), a novel lanthanum-manganese binary oxide (L1M2BO) adsorbent was synthesized by a simple oxidation coupled with precipitation method. The as-prepared L1M2BO was detailedly characterized by the XRD, SEM, TEM, BET, FTIR and XPS techniques. It is amorphous and irregular in shape, with a particle size of 50-100 nm and a specific surface area of 180.4 m2/g. A remarkable synergistic effect between the lanthanum hydroxide and Mn oxide in improving antimony adsorption is shown. The maximum adsorption capacities of Sb(III) and Sb(V) are 364.6 mg/g and 131.1 mg/g at pH 7.0, respectively, which outcompete most of reported adsorbents. The adsorption behaviors of antimony fitted well the pseudo-second-order kinetic and Freundlich models. The adsorption mechanism of Sb(V) involves mainly the replacement of surface metal hydroxyl and forming inner-sphere complex. While the Sb(III) removal is a more complicated process, containing both Sb(III) adsorption and oxidation to Sb(V). Furthermore, the spent L1M2BO sorbent can be regenerated and reused. The L1M2BO could be used as an attractive adsorbent for antimony removal, owing to its easily fabrication, high effectiveness and reusability.

Oil/water separation using elastic bio-aerogels derived from bagasse: Role of fabrication steps.

Bio-aerogels hold great promise for selective oil separation from water due to their light weight and high sustainability. However, how the fabrication methods impact the elasticity and oil sorption performance of bio-aerogels still needs systematic comparison and in-depth investigation. In this study, the fabrication of hydrophobic bio-aerogels with good elasticity and reusability was optimized using a factorial design based on the dosages of bagasse-derived cellulose nanofiber, sodium alginate, and calcium carbonate. The role of each key fabrication step, including ice-templating, calcium crosslinking, solvent dehydration, freeze-drying, and silanization, played in the material properties was also elucidated. The optimized bio-aerogels had a low density (7.55 mg/cm3), high porosity (99.47%), large specific surface area (39 m2/g), and strong hydrophobicity (water contact angle of 135°). In addition, the bio-aerogels exhibited outstanding selective oil separation ability towards the oil-water mixture, with oil sorption capacity of 89-126 times its weight. The in-situ calcium crosslinking and solvent dehydration were vital to create porosity and preserve the microstructure of the bio-aerogels. The chemical vapor deposition rendered the bio-aerogels hydrophobic and oleophilic, greatly enhancing the separability of oil from the water-oil mixture.

Confining Nano-Fe3O4 in the Superhydrophilic Membrane Skin Layer to Minimize Internal Fouling.

Membrane surface fouling is often reversible as it can be mitigated by enhancing the crossflow shear force. However, membrane internal fouling is often irreversible and thus more challenging. In this study, we developed a new superhydrophilic poly(vinylidene fluoride) (P-PVDF) membrane confined with nano-Fe3O4 in the top skin layer via reverse filtration to reduce internal fouling. The surface of the P-PVDF membrane confined with nano-Fe3O4 had superwetting properties (water contact angle reaching 0° within 1 s), increased roughness (from 182 to 239 nm), and enhanced water affinity. The Fe3O4@P-PVDF membrane surface showed a thicker and enhanced hydration layer, which prevented foulants from approaching membrane surfaces and pores, thereby improving the rejection. For example, when 50 ppm humic acid (HA) solution was used as the feed, the removal efficiency of the Fe3O4@P-PVDF membrane was ∼67%, while the HA removal of the P-PVDF membrane was only ∼20%. The results from the resistance-in-series model showed that nanoconfinement of Fe3O4 in the top skin layer of the membrane allowed foulants to accumulate on the membrane surface (i.e., surface fouling) rather than within the internal pores (i.e., internal fouling). The filtration results under crossflow fouling and cleaning confirmed that the Fe3O4@P-PVDF membrane had higher surface fouling but it was much more reversible and much lower internal fouling compared with the control membrane. Our fouling analysis offers new insights into mass transfer mechanisms of the membrane with a nanoconfinement-enhanced hydration layer. This study provides an effective strategy to develop membranes with low internal fouling propensities.

Highly efficient removal of thallium(I) by facilely fabricated amorphous titanium dioxide from water and wastewater.

In this study, amorphous hydrous titanium dioxide was synthesized by a facile precipitation method at room temperature, aiming to effectively remove thallium(I) from water. The titanium dioxide prepared using ammonia as precipitant (TiO2I) is more effective for thallium(I) uptake than the one synthesized with sodium hydroxide (TiO2II). The TiO2 obtained particles are amorphous, aggregates of many nanoparticles and irregular in shape. The thallium(I) uptake increases with the rise of solution pH value. Under neutral pH conditions, the maximal thallium(I) adsorption capacities of TiO2I and TiO2II are 302.6 and 230.3 mg/g, respectively, outperforming most of the reported adsorbents. The amorphous TiO2 has high selectivity towards thallium(I) in the presence of multiple cations such as K+, Ca2+, Mg2+, Zn2+ and Ni2+. Moreover, the TiO2I is efficient in removing thallium(I) from real river water and mining wastewater. Additionally, the spent TiO2I can be regenerated using hydrochloric acid solution and reused. The Tl(I) adsorption is achieved via replacing the H+ in hydroxyl group on the surface of TiO2 and forming inner-sphere surface complexes. Owing to its high efficiency, facile synthesis and environmental friendliness, the TiO2I has the potential to be used as an alternative adsorbent to remove Tl(I) from water.

Multi-step purification of electrolytic manganese residue leachate using hydroxide sedimentation, struvite precipitation, chlorination and coagulation: Advanced removal of manganese, ammonium, and phosphate.

Water pollution caused by the release of manganese (Mn2+) and ammonia nitrogen (NH4+-N) from electrolytic manganese residue (EMR) generated from industrial activities poses a serious threat to ecosystems and human health. In this study, an integrated process consisting sequentially of hydroxide sedimentation, struvite precipitation, breakpoint chlorination, and ferric chloride coagulation was optimized to remove Mn2+ and NH4+-N from EMR leachate, and to address the issue of residual orthophosphate caused by struvite precipitation. The precipitates were characterized using X-ray diffraction, scanning electron microscopy, and thermogravimetric analyses. Results show that Mn2+ ions and the resulting chemical oxygen demand (COD) were mainly removed using hydroxide precipitation at a sedimentation pH of 10.2, with poor-crystalline manganese hydroxide as the main precipitate. NH4+-N was primarily removed and recovered using struvite precipitation with well crystalline struvite as the main product, and then further eliminated using breakpoint chlorination. The residual orthophosphate introduced by struvite precipitation is successfully removed with ferric coagulation, and the effluent pH (7.5) is also lowered to discharge limits by means of hydrolysis of ferric coagulant. The concentration of COD, Mn2+, NH4+-N, and orthophosphate concentrations in the final effluent were 30.52 ± 9.38, 0.026 ± 0.013, 0.87 ± 0.01, and 0.06 ± 0.002 mg/L, respectively, meeting all local discharge standards. This combined process has robust pollutant removal efficiency, high resource recovery potential and few environmental constraints; thus, it is recommended as a potential solution for the treatment of Mn2+- and NH4+-N-rich acid mine drainage.

Uptake, organ distribution and health risk assessment of potentially toxic elements in crops in abandoned indigenous smelting region.

Inorganic pollution induced by smelting waste has threatened the safety of environment, whereas the impacts on farmlands with regards to potentially toxic elements (PTEs) receive insufficient attention. Herein, the contents, transfer pathways and potential risks of the PTEs in common crops were examined from different farmlands distributed around an indigenous Zn-smelting area in Guizhou, China. The results showed that Tl in cabbage (Brassica oleracea L.) (up to 3.74 mg/kg) and radish (Raphanus sativus L.) (up to 1.16 mg/kg) at some sites exceeded the maximum permissible level (MPL) (0.5 mg/kg) for food, and, under the same pollution condition, cabbage and radish were more likely to enrich PTEs, and the edible portion of maize was not prone to Tl risk. Hazard quotient calculations of Tl, Ba, and U were greater than 1, indicating the edible risk of crops for these PTEs. Further characterization of selected soils revealed that MnFe2O4 and Fe2O3 controlled the phase transformation of Tl(III) in rhizospheric soils. Furthermore, distinctive mullite was detected in the soil which confirmed the contribution of high temperature smelting to PTEs pollution. The findings indicate an emergent need for soil remediation around historical indigenous metal smelting areas for the sake of food security.

Efficient Sorption of Arsenic on Nanostructured Fe-Cu Binary Oxides: Influence of Structure and Crystallinity.

To study the structure-performance relationship, a series of nanostructured Fe-Cu binary oxides (FCBOs) were prepared by varying synthesis conditions. The obtained binary oxides were well characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET), magnetic and Zeta potential measurement techniques. Both As(V) and As(III) sorption on the FCBOs were evaluated by batch tests. Results show that the surface structure and crystallinity of FCBOs are greatly dependent on preparation conditions. The crystallinity of FCBOs gradually increases as the synthesis pH value increasing from 9.0 to 13.0, from amorphous phase to well-crystalline one. Simultaneously, the morphology change of FCBOs from irregular agglomerate to relatively uniform polyhedron has been observed. The sorption of arsenic is greatly influenced by the crystallinity and structure of FCBOs, decreasing with increasing degree of crystallinity. The amorphous FCBO has higher surface hydroxyl density than well-crystalline one, which might be the reason of higher sorption performance. As(V) is sorbed by the FCBOs via formation of inner-sphere surface complexes and As(III) is sorbed through formation of both inner- and outer-sphere surface complexes. This investigation provides new insights into structure-performance relationship of the FCBO system, which are beneficial to develop new and efficient sorbents.

Highly efficient removal of thallium(I) from wastewater via hypochlorite catalytic oxidation coupled with adsorption by hydrochar coated nickel ferrite composite.

In this study, tannery wastewater was used as carbon source to hydrothermally synthesize magnetic carbon-coated nickel ferrite composite (NiFe2O4@C), which was employed as a catalyst for thallium (Tl) oxidation by hypochlorite and simultaneously as an adsorbent for Tl removal from wastewater. Compared with NiFe2O4@C adsorption or hypochlorite oxidation alone, the combination of NiFe2O4@C and hypochlorite substantially enhanced the rate and efficiency of Tl(I) removal. In addition, this process was highly effective for Tl(I) removal over a wide pH range (6-12). The maximum Tl(I) removal capacity was 1699 mg/g at pH 10, which is the highest one reported so far. Electron spin resonance spectra suggested the formation of hypochlorite-based free radicals induced by the NiFe2O4@C composite, which enhanced the Tl(I) oxidation and removal. Oxidation-induced surface precipitation and surface complexation were found to be the main Tl(I) removal mechanisms. Consecutive cyclic regeneration tests implied robust regeneration and reuse performance of the composite. Moreover, it was effective for Tl(I) removal from real industrial wastewater. Therefore, the hypochlorite catalytic oxidation coupled with adsorption by the magnetic NiFe2O4@C composite is a promising technique for Tl(I) removal from wastewater. This hybrid process also has great potential for the removal of other pollutants.

Zero-valent iron-manganese bimetallic nanocomposites catalyze hypochlorite for enhanced thallium(I) oxidation and removal from wastewater: Materials characterization, process optimization and removal mechanisms.

Nano zero-valent metals adsorption coupled with advanced oxidation for environmental pollutants removal has been gaining attention recently. In this study, zero-valent iron-manganese (nZVIM) bimetallic nanocomposites were prepared via one-pot borohydride reduction and coupled with hypochlorite (ClO-) oxidation for enhanced thallium (Tl) removal from wastewater. Amorphous nZVIM nanoparticles were successfully synthesized, with a specific surface area of 106.89 m2/g, and a saturation magnetization of 65.16 emu/g. In comparison with the nZVIM adsorption or ClO- oxidation alone, the hybrid nZVIM/ClO- process achieved much faster Tl(I) removal rate over a wide pH range from 6 to 10. Maximum Tl(I) removal capacity was as high as 990.0 mg/g. The oxidation-induced adsorption for Tl(I) removal well followed the pseudo-first kinetic order model. Stable and effective adsorbent regeneration was achieved during the cyclic adsorption-desorption tests. This process also had high resistance to the interference of external cations, can act as an effective pretreatment for Tl(I) removal from the actual saline industrial wastewater. The main mechanisms for Tl(I) removal were found to be oxidation, surface precipitation, pore retention, and surface complexation. The nZVIM coupled with ClO- approach has great potential for Tl(I) removal from wastewater, and its application in other fields is highly anticipated.

Carbon quantum dots derived from the extracellular polymeric substance of anaerobic ammonium oxidation granular sludge for detection of trace Mn(vii) and Cr(vi).

Carbon quantum dots (CQDs) were synthesized via a hydrothermal method, in which extracellular polymeric substance (EPS) from anaerobic ammonium oxidation (anammox) granular sludge was used as a carbon precursor, while citric acid and ethylenediamine were applied as auxiliary carbon source and passivation agent, respectively. The synthesized CQDs, with orderly spherical shape and mean size of 7.15 nm, emitted blue fluorescent light under UV radiation of 365 nm. The CQDs had a high fluorescence yield (40.84%), with good water solubility and excellent spectroscopic properties. In addition, the CQDs exhibited selective, sensitive and distinctive fluorescence quenching behaviors for Cr(vi) and Mn(vii) in a PBS buffer solution (NaH2PO4-Na2HPO4) of pH 7, with a detection limit of 5.8 nM for Cr(vi) and 2.3 nM for Mn(vii). Owing to the nitrogen components from the EPS of anammox granules, the CQDs were well nitrogen-doped, promoting electron-transfer and leading to reduction between the CQDs and Mn(vii)/Cr(vi). These results indicate that CQD-based chemical sensing is a simple and efficient means for the fluorescence detection of Mn(vii) and Cr(vi).

Enhanced thallium(I) removal from wastewater using hypochlorite oxidation coupled with magnetite-based biochar adsorption.

The development of efficient and regenerable adsorbent coupled with advanced oxidation for enhanced thallium (Tl) removal has been a recent focus on wastewater treatment. In this study, a magnetite-based biochar derived from watermelon rinds was synthesized and used as a sustainable adsorbent and catalyst for hypochlorite oxidation and removal of Tl(I) from wastewater. The addition of hypochlorite substantially enhanced the Tl(I) removal under normal pH range (6-9). Maximum Tl adsorption capacity of 1123 mg/g was achieved, which is 12.3% higher than the highest value previously reported. The magnetic biochar can be regenerated using 0.1 mol/L HNO3 solution for elution in only 5 min, with a Tl desorption efficiency of 78.9%. The Tl removal efficiency was constantly higher than 98.5% during five consecutive recycle tests, indicating the effective reuse performance of the adsorbent. Oxidation, surface precipitation, pore retention and surface complexation were the main mechanisms for Tl(I) removal. The re-dissolution of Tl compounds and ion exchange of Tl cations with proton were the main mechanisms for adsorbent regeneration. Given the fast oxidation rate, high adsorption capacity, steady reusability and facile separability, this magnetic biochar-hypochlorite technique is a promising means for Tl(I) removal from wastewater. The catalytic hypochlorite oxidation induced by the magnetic biochar has also great potential to the effective removal of other pollutants.

Polyvinyl alcohol-stabilized granular Fe-Mn binary oxide as an effective adsorbent for simultaneous removal of arsenate and arsenite.

A novel granular Fe-Mn (GFM) binary oxide sorbent, with a diameter of approximate 2.0 mm and a length of 2.0-3.0 mm, was successfully prepared using extrusion granulation method in this study. The GFM sorbent is highly porous with a BET-specific surface area of 210.3 m2/g. It shows high effectiveness in simultaneously adsorbing As(V) and As(III). The maximal sorption capacities for As(V) and As(III) are 33.2 and 50.7 mg/g at pH 7.0 ± 0.1, respectively, which are superior to most of granular sorbents reported in the literature. The present Ca2+, Mg2+, humic acids and fulvic acids do not have obvious influence on the arsenic sorption. But, coexisting anions affect negatively arsenic sorption in the following order: H2PO4 - > SiO3 2- > HCO3 - > SO4 2-. NaOH solution is an effective eluent for regeneration of the arsenic-loaded GFM. The GFM packed in the fixed-bed column can treat approximately 3400 and 6500 bed volumes of simulated groundwater containing 233 µg/L As(V) and As(III), respectively, before the arsenic concentration in the effluent reached a drinking water limit of 10 µg/L. The features of high effectiveness, selectivity and reusability make the GFM a potential alternative to remove simultaneously As(V) and As(III) from groundwater.

Hyperaccumulation and transport mechanism of thallium and arsenic in brake ferns (Pteris vittata L.): A case study from mining area.

Both thallium (Tl) and arsenic (As) bear severe toxicity. Brake fern (Pteris vittata L.) is well-known for its hyperaccumulation capacity of As, yet its role on Tl accumulation remains unknown. Herein, brake ferns growing near an As tailing site in Yunnan, Southwestern China are for the first time discovered as a co-hyperaccumulator of both Tl and As. The results showed that the brake ferns extracted both As and Tl efficiently from the soils into the fronds. The studied ferns growing on Tl and As co-polluted soils were found to accumulate extremely high levels of both As (7215-11110 mg/kg) and Tl (6.47-111 mg/kg). Conspicuously high bio-accumulation factor (BCF) was observed for As (7.8) and even higher for Tl (28.4) among these co-hyperaccumulators, wherein the contents of As and Tl in contaminated soils were 1240 ± 12 and 3.91 ± 0.01 mg/kg, respectively. The applied advanced characterization techniques (e.g. transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS)) indicated a preferential uptake of Tl(I) while simultaneous accumulation of As (III) and As(V) from the Tl(I)/Tl(III)-As (III)/As(V) co-existent rhizospheric soils. The findings benefit the phytoremediation practice and pose implications for managing and restoring Tl-As co-contaminated soils in other countries.

Synthesis of manganese dioxide with different morphologies for thallium removal from wastewater.

Manganese dioxide (MnO2) with different morphologies (tube-, wire-, rod-, and flower-like) was synthesized via hydrothermal method and then applied for thallium (Tl) removal from wastewater. During material synthesis, short reaction time (6 h) and low temperature (110 °C) were prone to form polycrystalline flower-like birnessite type MnO2, while long reaction time (24 h) and high temperature (240 °C) were inclined to produce polycrystalline wire-like birnessite type MnO2. Moderate reaction time (12 h) with low temperature at 120 °C/140 °C led to formation of mono-crystalline rod- and tube-like α-MnO2, respectively. Wire-like MnO2 was the most effective adsorbent for Tl(I) removal from both the synthetic and industrial wastewaters. The MnO2 of four morphologies exhibited similarly high Tl(III) removal owing to the precipitation of Tl(III) as Tl2O3. Effective Tl(I)/Tl(III) removal (99%) was achieved with wire-like MnO2 at an initial pH of 6 and an adsorbent dosage of 0.25 g/L. The Tl(I)/Tl(III) adsorption can be described with the pseudo-second-order kinetic. The Tl(I) removal was best fitted with the Freundlich model, with a maximum adsorption capacity of 450 mg/g. While the Tl(III) removal was best fitted with the Langmuir model, with an extremely high capacity of 6250 mg/g. Based on the results from XRD, SEM-EDS, FT-IR, and XPS analyses, the mechanisms of Tl removal using wire-like MnO2 are primarily surface complexation and oxidative precipitation. Overall, wire-like MnO2 is a highly effective adsorbent for Tl removal from both synthetic and actual wastewaters.