Key role of sulfur in sulfidated zerovalent iron during persulfate activation for the dynamic equilibrium of oxidative radicals including SO4•- and •OH.

Surface sulfidation has been widely investigated to effectively enhance the utilization and selectivity of iron electrons for enhanced pollutant reduction. However, there is relatively less knowledge on whether sulfidation facilitates the catalytic oxidation process and the mechanism of enhancement. Therefore, in this study, the role of surface sulfidation in modulating the oxidant decomposition pathway and reactive oxygen species generation was investigated with the sulfidated zerovalent iron (S-ZVI) activated persulfate (PS) system. The results revealed that sulfur on the surface of S-ZVI not only facilitates PS activation to generate more SO4•-, but also acts as an essential in the dynamic equilibrium between SO4•- and •OH. Specifically, the S-ZVI surface sulfide first forms sulfur monomers during catalysis, which promotes electron transfer to accelerate Fe3+ to Fe2+ cycling, prompting the generation of more SO4•- also generates SO32-. Then, SO32- is further reacted with •OH to generate the [O--O-SO3-] intermediate of SO4•-, which leads to a dynamic equilibrium of SO4•- and •OH, mitigating the further conversion of SO4•- to •OH. These findings unveiled the dynamic variation of sulfur on the surface of S-ZVI during PS activation, elevating new insights for the sulfate radical-based efficient degradation.

Highly stable carbon-coated nZVI composite Fe0@RF-C for efficient degradation of emerging contaminants.

Nanoscale zerovalent iron (nZVI) has garnered significant attention as an efficient advanced oxidation activator, but its practical application is hindered by aggregation and oxidation. Coating nZVI with carbon can effectively addresses these issues. A simple and scalable production method for carbon-coated nZVI composite is highly desirable. The anti-oxidation and catalytic performance of carbon-coated nZVI composite merit in-depth research. In this study, a highly stable carbon-coated core-shell nZVI composite (Fe0@RF-C) was successfully prepared using a simple method combining phenolic resin embedding and carbothermal reduction. Fe0@RF-C was employed as a heterogeneous persulfate (PS) activator for degrading 2,4-dihydroxybenzophenone (BP-1), an emerging contaminant. Compared to commercial nZVI, Fe0@RF-C exhibited superior PS activation performance and oxidation resistance. Nearly 95% of BP-1 was removed within 10 min in the Fe0@RF-C/PS system. The carbon layer promotes the enrichment of BP-1 and accelerates its degradation through singlet oxygen oxidation and direct electron transfer processes. This study provides a straightforward approach for designing highly stable carbon-coated nZVI composite and elucidates the enhanced catalytic performance mechanism by carbon layers.

Enhancing and sustaining arsenic removal in a zerovalent iron-based magnetic flow-through water treatment system.

In areas affected by arsenicosis, zerovalent iron (ZVI)/sand filters are extensively used by households to treat groundwater, but ZVI surface passivation and filter clogging limit their arsenic (As) removal performance. Here we present a magnetic confinement-enabled column reactor coupled with periodic ultrasonic depassivation (MCCR-PUD), which efficiently and sustainably removes As by reaction with continuously generated iron (oxyhydr)oxides from ZVI oxidative corrosion. In the MCCR, ZVI microparticles self-assemble into stable millimeter-scale wires in forest-like arrays in a parallel magnetic field (0.42-0.48 T, produced by two parallel permanent magnets), forming a highly porous structure (87 % porosity) with twice the accessible reactive surface area of a ZVI/sand mixture. For a feed concentration of 100 µg/L As(III), the MCCR-PUD, with a short empty bed contact time (1.6 min), treated ca. 7340 empty bed volume (EBV) of water at breakthrough (10 µg/L), 9.4 folds higher than that of a ZVI/sand filter. Due to the large interspace between ZVI wires, the MCCR-PUD effectively prevented column clogging that occurred in the ZVI/sand filter. The high water treatment capacity was attributed to the much enhanced ZVI reactivity in the magnetic field, sustained through rejuvenation by PUD. Furthermore, most of As was structurally incorporated into the produced iron (oxyhydr)oxides (mostly ferrihydrite) in the MCCR-PUD, as revealed by Mössbauer spectroscopy, X-ray absorption spectroscopy, and sequential extraction experiments. This finding evinced a different mechanism from the surface adsorption in the ZVI/sand filter. The structural incorporation of As also resulted in much less As remobilization from the produced corrosion products during aging in water, in total ∼1 % in 28 days. Furthermore, the MCCR-PUD exihibted robust performance when treating complex synthetic groundwater containing natural organic matter and common ions (∼3700 EBV at breakthrough). Taken together, our study demonstrates the potential of the magnetic confinement-enabled ZVI reactor as a promising decentralized As treatment platform.

Rapid Oxidative Dissolution of Zerovalent Iron Induced by Sulfite for Efficient Removal of Arsenate and Arsenite: Selective Formation of Scorodite.

In this study, we proposed a moderate oxidation strategy for accelerating the oxidative dissolution of zerovalent iron (ZVI) using sulfite (S(IV)), thereby improving the removal of As(V) and As(III). Results revealed that, in the presence of 2.0 mM S(IV), both As(V) and As(III) were selectively converted into scorodite at pH0 3.0-7.0, while As(III) oxidation and As(V) immobilization were impressed over pH0 8.0-10.0. Batch experiments, radical quenching experiments, and electron spin resonance (ESR) measurements demonstrated that ZVI initially boosted S(IV) activation to generate SO4•-, •OH, and protons, and in turn, ZVI was further oxidized more intensely by these radicals than by oxygen. Concurrently, substantial protons derived from S(IV) oxidation neutralized hydroxyls produced by ZVI oxidation, maintaining an acidic environment conducive to the generation of scorodite rather than iron (hydr)oxides. Characterizations of X-ray diffraction (XRD), Raman, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM) confirmed that scorodite was formed in situ and then exfoliated from the surface of ZVI, and approximately 75% of ZVI could still be recovered, which contributed to efficient As removal in successive runs and real As-polluted wastewater. The application of S(IV) achieved a balance among ZVI reactivity improvement, As(V)/As(III) removal, and raw material consumption, making it a promising approach for addressing arsenic contamination in wastewater treatment.

Iron Nanostructure Primes Arbuscular Mycorrhizal Fungi Symbiosis Tightly Connecting Maize Leaf Photosynthesis via a Nanofilm Effect.

It is crucial to clarify how the iron nanostructure activates plant growth, particularly in combination with arbuscular mycorrhizal fungi (AMF). We first identified 1.0 g·kg-1 of nanoscale zerovalent iron (nZVI) as appropriate dosage to maximize maize growth by 12.7-19.7% in non-AMF and 18.9-26.4% in AMF, respectively. Yet, excessive nZVI at 2.0 g·kg-1 exerted inhibitory effects while FeSO4 showed slight effects (p > 0.05). Under an appropriate dose, a nano core-shell structure was formed and the transfer and diffusion of electrons between PS II and PS I were facilitated, significantly promoting the reduction of ferricyanide and NADP (p < 0.05). SEM images showed that excessive nZVI particles can form stacked layers on the surface of roots and hyphae, inhibiting water and nutrient uptake. TEM observations showed that excessive nanoparticles can penetrate into root cortical cells, disrupt cellular homeostasis, and substantially elevate Fe content in roots (p < 0.05). This exacerbated membrane lipid peroxidation and osmotic regulation, accordingly restricting photosynthetic capacity and AMF colonization. Yet, appropriate nZVI can be adhered to a mycelium surface, forming a uniform nanofilm structure. The strength of the mycelium network was evidently enhanced, under an increased root colonization rate and an extramatrical hyphal length (p < 0.05). Enhanced mycorrhizal infection was tightly associated with higher gas exchange and Rubisco and Rubisco enzyme activities. This enabled more photosynthetic carbon to input into AMF symbiont. There existed a positive feedback loop connecting downward transfer of photosynthate and upward transport of water/nutrients. FeSO4 only slightly affected mycorrhizal development. Thus, it was the Fe nanostructure but not its inorganic salt state that primed AMF symbionts for better growth.

Equilibrium and kinetic modeling of Cr(VI) removal by novel tolerant bacteria species along with zero-valent iron nanoparticles.

This work describes the study of the removal of a refractory contaminant, i.e., Hexavalent chromium (Cr(VI)) from aqueous systems by a novel adsorbent comprising Cr(VI) tolerant bacteria and zero valent iron nanoparticle (nZVI). A gram-positive, rod-shaped bacteria used in the study were isolated from wastewater (WW) received from the effluent of leather industries. The adsorbents were prepared with bacteria, nZVI alone, and a combination of both. The adsorbent comprising both elements was found to remove Cr(VI) with a higher percentage (93%) and higher capacities (0.58 mg/g) as compared to adsorbent with bacteria (Cr(VI) removal = 63%, qe = 0.163 mg/g) or nanoparticles (Cr(VI) removal = 80%, qe = 0.45 mg/g) alone. The adsorbent worked best at neutral pH, and the removal became saturated after 90 min of incubation. Equilibrium studies with isotherm modeling suggested that the adsorption process follows sips isotherm (R2 = 0.9955), which is expected to bean intra-particle diffusion process before the actual adsorption. Process kinetics was modeled with pseudo-first order, pseudo-second order, and Vermeulen model. The diffusion coefficient determined by fitting the kinetic data to Vermeulen model was found to be 0.0000314 cm2/s. The adsorbent can be tested further for continuous flow processes to find more insights about the usage on a large scale.

Biomass-derived cellulose nanocrystals modified nZVI for enhanced tetrabromobisphenol A (TBBPA) removal.

Nano zero-valent iron (nZVI) is an advanced environmental functional material for the degradation of tetrabromobisphenol A (TBBPA). However, high surface energy, self-agglomeration and low electron selectivity limit degradation rate and complete debromination of bare nZVI. Herein, we presented biomass-derived cellulose nanocrystals (CNC) modified nZVI (CNC/nZVI) for enhanced TBBPA removal. The effects of raw material (straw, filter paper and cotton), process (time, type and concentration of acid hydrolysis) and synthesis methods (in-situ and ex-situ) on fabrication of CNC/nZVI were systematically evaluated based on TBBPA removal performance. The optimized CNC-S/nZVI(in) was prepared via in-situ liquid-phase reduction using straw as raw material of CNC and processing through 44 % H2SO4 for 165 min. Characterizations illustrated nZVI was anchored to the active sites at CNC interface through electrostatic interactions, hydrogen bonds and FeO coordinations. The batch experiments showed 0.5 g/L CNC-S/nZVI(in) achieved 96.5 % removal efficiency at pH = 7 for 10 mg/L initial TBBPA. The enhanced TBBPA dehalogenation by CNC-S/nZVI(in), involving in initial adsorption, reduction process and partial detachment of debrominated products, were possibly attributed to elevated pre-adsorption capacity and high-efficiency delivery of electrons synergistically. This study indicated that fine-tuned fabrication of CNC/nZVI could potentially be a promising alternative for remediation of TBBPA-contaminated aquatic environments.

Insight into the catalytic performances of Fe0@chitosan/cellulose green hybrid structure for enhanced photo-Fenton's oxidation of levofloxacin toxic residuals: Pathway and toxicity.

A green hybridized structure of Fe0 painted chitosan/cellulose base (Fe0@CS/CF) has been developed using cellulose extracted from sugarcane bagasse along with reduction agents sourced from Khaya senegalensis leaves. The composite was assessed as an affordable, powerful, and multifunctional catalyst for enhancing the degradation of Levofloxacin (LVX) remnants within water supplies via photo-Fenton's interactions. Using a dosage of 0.5 g/L, the Fe0@CS/CF blend demonstrated noteworthy catalytic qualities, resulting in the complete photo-Fenton's degradation of LVX at a level of 25 mg/L after 40 min. However, the complete diminution of organic carbon (TOC) occurred only after 100 min, suggesting the presence of significant intermediate residues. The identified intermediate chemicals and confirmed hydroxyl radicals as the main oxidizer suggest that the degradation pathway involves carboxylation/decarboxylation, hydroxylation, demethylation, and oxidation of quinolone rings. The toxicity properties of untreated LVX solutions and their subsequent oxidized byproducts were assessed by evaluating their inhibiting impact on Vibrio fischeri over various durations. The samples that experienced partial oxidation at initial testing demonstrated a higher level of toxicity in comparison to the parent LVX. However, the sample that was treated for 100 min demonstrated substantial biological safety and a non-toxic nature. The blend of ingredients has a synergistic impact that enhances the uptake, Fenton's, photocatalytic, and photo-Fenton's characteristics of the hosted Fe0 nanoparticles.

Carboxymethyl cellulose stabilization induced changes in particle characteristics and dechlorination efficiency of sulfidated nanoscale zero-valent iron.

Polymer stabilization, exemplified by carboxymethyl cellulose (CMC), has demonstrated effectiveness in enhancing the transport of nanoscale zero-valent iron (nZVI). And, sulfidation is recognized for enhancing the reactivity and selectivity of nZVI in dechlorination processes. The influence of polymer stabilization on sulfidated nZVI (S-nZVI) with various sulfur precursors remains unclear. In this study, CMC-stabilized S-nZVI (CMC-S-nZVI) was synthesized using three distinct sulfur precursors (S2-, S2O42-, and S2O32-) through one-step approach. The antioxidant properties of CMC significantly elevated the concentration of reduced sulfur species (S2-) on CMC-S-nZVIs, marking a 3.1-7.0-fold increase compared to S-nZVIs. The rate of trichloroethylene degradation (km) by CMC-S-nZVIs was observed to be 2.2-9.0 times higher than that achieved by their non-stabilized counterparts. Among the three CMC-S-nZVIs, CMC-S-nZVINa2S exhibited the highest km. Interesting, while the electron efficiency of CMC-S-nZVIs surged by 7.9-12 times relative to nZVI, it experienced a reduction of 7.0-34% when compared with S-nZVIs. This phenomenon is attributed to the increased hydrophilicity of S-nZVI particles due to CMC stabilization, which inadvertently promotes the hydrogen evolution reaction (HER). In conclusion, the findings of this study underscores the impact of CMC stabilization on the properties and dechlorination performance of S-nZVI sulfidated using different sulfur precursors, offering guidance for engineering CMC-S-nZVIs with desirable properties for contaminated groundwater remediation.

Green cleanup of styrene-contaminated soil by carbon-based nanoscale zero-valent iron and phytoremediation: Sunn hemp (Crotalaria juncea), zinnia (Zinnia violacea Cav.), and marigold (Tagetes erecta L.).

Accidental chemical spills can result in styrene-contaminated soil. Styrene negatively affects human health and the environment. The objective of this study was to remediate styrene-contaminated soil using a combination of activated carbon-based nanoscale zero-valent iron (nZVI-AC) and phytoremediation by sunn hemp (Crotalaria juncea), zinnia (Zinnia violacea Cav.) and marigolds (Tagetes erecta L.). The results showed that all three plant types could potentially increase the removal efficiency of styrene-contaminated soil. At 28 days, all three plants showed complete removal of styrene from the soil with 1 g/kg of nZVI-AC, activated carbon-based nZVI synthesized by tea leaves (Camellia sinensis) (T-nZVI-AC), or activated carbon-based nZVI synthesized by red Thai holy basil (Ocimum tenuiflorum L.) (B-nZVI-AC). However, styrene removal efficiencies of sunn hemp, zinnia, and marigold without carbon-based nZVI were 30%, 67%, and 56%, respectively. Statistical analysis (ANOVA) revealed that the removal efficiencies differed significantly from those of phytoremediation alone. With the same removal efficiency (100%), the biomass of sunn hemp in nano-phytoremediation treatments differed by approximately 55%, whereas the biomass of zinnia differed by >67%, compared with that of the control experiment. For marigold, the difference in biomass was only 30%. Styrene was adsorbed on surface of soil and AC and then further oxidized under air-water-nZVI environment, while phytovolatilization played an important role in transporting the remaining styrene from the contaminated soil to the air. Marigold was used as an alternative plant for the nano-phytoremediation of styrene-contaminated soil because of its sturdy nature, high biomass, tolerance to toxic effects, and ease of cultivation. Remediation of one cubic meter of styrene-contaminated soil by a combination of carbon-based nanoscale zero-valent iron and phytoremediation by marigolds emitted 0.0027 kgCO2/m3.

Exploring the synergistic effect of chromium (Cr) tolerant Pseudomonas aeruginosa and nano zero valent iron (nZVI) for suppressing Cr uptake in Aloe Vera.

Chromium (Cr) contamination of soil has substantially deteriorated soil health and has interfered with sustainable agricultural production worldwide and therefore, its remediation is inevitable. Inoculation of plant growth promoting rhizobacteria (PGPR) in association with nanotechnology has exerted broad based impacts in agriculture, and there is an urgent need to exploit their synergism in contaminated soils. Here, we investigated the effect of co-application of Cr-tolerant "Pseudomonas aeruginosa CKQ9" strain and nano zerovalent iron (nZVI) in improving the phytoremediation potential of aloe vera (Aloe barbadensis L.) under Cr contamination. Soil was contaminated by using potassium dichromate (K2Cr2O7) salt and 15 mg kg-1 contamination level in soil was maintained via spiking and exposure to Cr lasted throughout the duration of the experiment (120 days). We observed that the co-application alleviated the adverse impacts of Cr on aloe vera, and improved various plant attributes such as plant height, root area, number of leaves and gel contents by 51, 137, 67 and 49% respectively as compared to control treatment under Cr contamination. Similarly, significant boost in the activities of various antioxidants including catalase (124%), superoxide dismutase (87%), ascorbate peroxidase (36%), peroxidase (89%) and proline (34%) was pragmatic under contaminated soil conditions. In terms of soil Cr concentration and its plant uptake, co-application of P. aeruginosa and nZVI also reduced available Cr concentration in soil (50%), roots (77%) and leaves (84%), while simultaneously increasing the relative production index by 225% than un-inoculated control. Hence, integrating PGPR with nZVI can be an effective strategy for enhancing the phytoremediation potential of aloe vera.

Combined effect of PGPR and nanotechnology in the bioremediation of toxic contaminants is well reported in literature. Most of these reports comprise the use of hyperaccumulator plants for phytoextraction of heavy metals. However, phytostabilization potential of hyperaccumulators is still un-explored. Current study investigated the role of PGPR and Fe-NPs in suppressing the uptake of Cr in aloe vera, a hyperaccumulator plant.

Hydrogen Nanobubbles Generated In Situ from Nanoscale Zerovalent Iron with Water to Further Enhance Selenite Sequestration.

Gas nanobubbles used for water treatment and recovery give rise to great concern for their unique advantages of less byproducts, higher efficiency, and environmental friendliness. Nanoscale zerovalent iron (nZVI), which has also been widely explored in the field of environmental remediation, can generate gas hydrogen by direct reaction with water. Whether nanoscale hydrogen bubbles can be produced to enhance the pollution removal of the nZVI system is one significant concern involved. Herein, we report direct observations of in situ generation of hydrogen nanobubbles (HNBs) from nZVI in water. More importantly, the formed HNBs can enhance indeed the reduction of Se(IV) beyond the chemical reduction ascribed to Fe(0), especially in the anaerobic environment. The possible mechanism is that HNBs enhance the reducibility of the system and promote electron transport in the solution. This study demonstrates a unique function of HNBs combined with nZVI for the pollutant removal and a new approach for in situ HNB generation for potential applications in the fields of in situ remediation agriculture, biotechnology, medical treatment, health, etc.

Efficient peroxymonosulfate activation by nanoscale zerovalent iron for removal of sulfadiazine and sulfadiazine resistance bacteria: Sulfidated modification or not.

Whether it's necessary to extra chemical synthesis steps to modify nZVI in peroxymonosulfate (PMS) activation process are worth to further investigation. The 56 mg/L nZVI/153.65 mg/L PMS and 56 mg/L sulfidated nZVI (S-nZVI) (S/Fe molar ratio = 1:5)/153.65 mg/L PMS) processes could effectively attain 97.7% (with kobs of 3.7817 min-1) and 97.0% (with kobs of 3.4966 min-1) of the degradation of 20 mg/L sulfadiazine (SDZ) in 1 min, respectively. The nZVI/PMS system could quickly achieve 85.5% degradation of 20 mg/L SDZ in 1 min and effectively inactivate 99.99% of coexisting Pseudomonas. HLS-6 (5.81-log) in 30 min. Electron paramagnetic resonance tests and radical quenching experiments determined SO4•-, HO•, 1O2 and O2•- were responsible for SDZ degradation. The nZVI/PMS system could still achieve the satisfactory degradation efficiency of SDZ under the influence of humic acid (exceeded 96.1%), common anions (exceeded 67.3%), synthetic wastewater effluent (exceeded 90.7%) and real wastewater effluent (exceeded 78.7%). The high degradation efficiency of tetracycline (exceeded 98.9%) and five common disinfectants (exceeded 96.3%) confirmed the applicability of the two systems for pollutants removal. It's no necessary to extra chemical synthesis steps to modify nZVI for PMS activation to remove both chemical and biological pollutants.

Reductive sequestration of Cr (VI) by phosphorylated nanoscale zerovalent iron.

The cracked phosphorylated nanoscale zerovalent iron (p-nZVI) has a strong electron selectivity towards the reductive removal of many heavy metal ions in waters. However, the unintended environmental risk after interactions with impurities or wastewater are not involved. Therefore, in this study, the phosphate group was successfully adsorbed into p-nZVI, and the cracked p-nZVI was successfully prepared with an optimal P/Fe ratio of 0.5%. The dosages of p-nZVI and temperatures were positively correlated with the removal rates. The removal process of Cr(VI) was more suitable by the Langmuir isothermal model（R2 > 0.99). The process of Cr (VI) (10, 20 and 40 mg/L) removal more fitted the pseudo first-order reaction model, while the process of Cr (VI) (60, 80 mg/L) removal more fitted the pseudo second-order reaction model. The Cr (VI) removal rates gradually decreased when the pH was increased. Dissolved oxygen slowed nanoiron reaction rates. The order of inhibition on the reactivity towards Cr(VI) was SiO32- > SO42- > PO43- > NO3- > HCO3-.The facilitation followed the order of Cd2+>Cu2+>Mg2+>Mn2+>Ca2+. Ca2+ showed an inhibitory effect, but all other cations showed different degrees of facilitation. The promotion effect is relatively similar in presence of Mn2+ or Mg2+. HA had a significant inhibitory effect. Environmental friendly p-nZVI had a good effect in simulated groundwater, seawater, river water and secondary effluent of the urban sewage treatment plant. The main pathway to remove Cr (VI) was in situ reduction by p-nZVI. The improved adsorption and reduction effect of p-nZVI on heavy metal ions in water was due to the structural change and the phosphate group.

Insights into the long-term immobilization performances and mechanisms of CMC-Fe0/FeS with different sulfur sources for uranium under anoxic and oxic aging.

Nanoscale zerovalent iron (Fe0)-based materials have been demonstrated to be a effective method for the U(VI) removal. However, limited research has been conducted on the long-term immobilization efficiency and mechanism of Fe0-based materials for U(VI), which are essential for achieving safe handling and disposal of U(VI) on a large scale. In this study, the prepared carboxymethyl cellulose (CMC) and sulfurization dual stabilized Fe0 (CMC-Fe0/FeS) exhibited excellent long-term immobilization performances for U(VI) under both anoxic and oxic conditions, with the immobilization efficiencies were respectively reached over 98.0 % and 94.8 % after 180 days of aging. Most importantly, different from the immobilization mechanisms of the fresh CMC-Fe0/FeS for U(VI) (the adsorption effect of -COOH and -OH groups, coordination effect with sulfur species, as well as reduction effect of Fe0), the re-mobilized U(VI) were finally re-immobilized by the formed FeOOH and Fe3O4 on the aged CMC-Fe0/FeS. Under anoxic conditions, more Fe3O4 was produced, which may be the main reason for the long-term immobilization U(VI). Under oxic conditions, the production of Fe3O4 and FeOOH were relatively high, which both played significant roles in re-immobilizing U(VI) through surface complexation, reduction and incorporation effects.

Chitosan anchored nZVI bionanocomposites for treatment of textile wastewater: Optimization, mechanism, and phytotoxic assessment.

In recent years, there has been a growing focus on treating textile wastewater due to its escalating threat to aquatic ecosystems and exposed communities. The present study investigates the adsorption efficacy of biopolymer functionalized nanoscale zero-valent iron (CS@nZVI) composite for the treatment of textile wastewater using the RSM-CCD model. The structure and morphology of CS@nZVI were characterized using XRD, FTIR, FESEM, and EDX. CS@nZVI was then evaluated for its adsorption potential in removing COD, color, and other physico-chemical parameters from textile wastewater. The results showed the high efficacy of CS@nZVI for COD and color removal from textile wastewater. Under optimal conditions (pH 6, contact time 60 min, and 1.84 g CS@nZVI), COD removal reached a maximum of 85.53%, and decolorization efficiency was found to be 89.73%. The coefficient of determination R2 (0.98) and AIC (269.75) values suggested quadratic model as the best-fitted model for optimizing the process parameters for COD removal. Additionally, the physico-chemical parameters were found to be within permissible limits after treatment with CS@nZVI. The influence of coexisting ions on COD removal followed the order PO43- > SO42- > Cl- >Na+ > Ca2+. The kinetics data fitted well with the pseudo-first-order reaction, indicating physisorption as the primary mechanism. The thermodynamic study revealed the endothermic nature of the removal process. Reusability tests demonstrated that great regeneration capacity of spent CS@nZVIafter five consecutive cycles. Furthermore, toxicological studies showed reduced toxicity in treated samples, leading to improved growth of Vigna radiata L. These findings suggest that CS@nZVI bionanocomposites could serve as an efficient, cost-effective, and eco-friendly remediation agent for the treatment of textile effluents, presenting significant prospects for commercial applications.

Performance evaluation of sulfidated nanoscale iron for hexavalent chromium removal from groundwater in sequential batch study.

Chromium [Cr] contamination in groundwater is one of the serious environmental concerns due to the carcinogenicity of its water-soluble and mobile hexavalent [Cr(VI)] form. In spite of the existence of multiple precipitation and adsorption-based Cr(VI) remediation technologies, the usage of sulfidated nano zerovalent iron (S-nZVI) has recently attracted researchers due to its high selectivity. Although S-nZVI effectively immobilized Cr(VI), its long-term performance in multiple shifted equilibrium has not been explored. In this contribution, influences of S-nZVI dosage, initial concentration of Cr(VI), pH, ionic strength, total hardness, sulfate, carbonate, and silicate were probed in ultrapure water. Further experiments were performed in synthetic groundwater to investigate the effects of initial concentration of Cr(VI) in the pH range of 4-8 for 1 g L-1 S-nZVI dosage. Cr(VI) removal rate was quantified in groundwater without pH fixation. Finally, a comparative study between conventional nano zerovalent iron (nZVI) and S-nZVI was conducted in sequential batch reactors to investigate their respective efficiencies during repeated usage. Mechanistic interpretation of the processes governing the immobilization of Cr(VI) was done by integrating the results of these experiments with the metadata. While aggregation due to magnetic properties and rapid oxidation of Fe decreased the efficiency of nZVI with repeated usage, sulfidation minimized the passivation and favored an extended reducing environment because of continuous electron transfer from iron and sulfur components.

Enhanced Biogenic Sulfidation of Zero-Valent Iron in Columns: Implications for Promoting Dechlorination in Permeable Reactive Barriers.

Biogenic sulfidation of zero-valent iron (ZVI) using sulfate reducing bacteria (SRB) has shown enhanced dechlorination rates comparable to those produced by chemical sulfidation. However, controlling and sustaining biogenic sulfidation to enhance in situ dechlorination are poorly understood. Detailed interactions between SRB and ZVI were examined for 4 months in column experiments under enhanced biogenic sulfidation conditions. SRB proliferation and changes in ZVI surface properties were characterized along the flow paths. The results show that ZVI can stimulate SRB activity by removing excessive free sulfide (S2-), in addition to lowering reduction potential. ZVI also hinders downgradient movement of SRB via electrostatic repulsion, restricting SRB presence near the upgradient interface. Dissolved organic carbon (e.g., >2.2 mM) was essential for intense biogenic sulfidation in ZVI columns. The presence of SRB in the upgradient zone appeared to promote the formation of iron polysulfides. Biogenic FeSx deposition increased the S content on ZVI surfaces ∼3-fold, corresponding to 3-fold and 2-fold improvements in the trichloroethylene degradation rate and electron efficiency in batch tests. Elucidation of SRB and ZVI interactions enhances sustained sulfidation in ZVI permeable reactive barrier.

Long-term stability and toxicity effects of three-dimensional electrokinetic remediation on chromium-contaminated soils.

The three-dimensional electrokinetic remediation (3D EKR) achieved efficient removal of chromium (Cr) from the soil through mechanisms including electromigration, electroosmosis, and redox reactions. In this study, the long-term stability, leaching toxicity, bioavailability, and phytotoxicity of Cr in remediated soils were systematically analyzed to comprehensively evaluate the effectiveness of the 3D EKR method. The results showed that the concentration of hexavalent chromium (Cr (VI)) in the leachate of the 3D EKR system with sulfidated nano-scale zerovalent iron (S-nZVI) was more than 40% lower than those of the other 3D electrode groups, and the time required to reach the level III standard of groundwater quality criterion in China (0.05 mg/L, GB/T 14848-2017) was significantly shortened. The stabilization of Cr(VI) in contaminated soil after 3D EKR was maintained for 300 pore volumes (PVs), indicating that the treated Cr(VI) had good long-term stability. The leaching toxicity and bioaccessibility of Cr were assessed by the synthetic precipitation leaching procedure (SPLP), the toxicity characteristic leaching procedure (TCLP), and the physiologically based extraction test (PBET). The concentration of Cr(VI) in the SPLP, TCLP, and PBET leachates of the S-nZVI group decreased by more than 25% compared to the other 3D electrode groups, corresponding to the decrease in leaching toxicity and bioavailability of the treated Cr during the 15-day remediation period. In addition, the germination rate of wheat seeds and the average biomass of wheat seedlings in the S-nZVI group under alkaline conditions (EE) were higher than those in the non-polluting group (Blank-OH), indicating that the remediated soil had no obvious toxicity to wheat. In summary, 3D EKR achieved a satisfactory and stable remediation effect on Cr-contaminated soil, especially when using S-nZVI as the 3D electrode.

Clean water production from plastic and heavy metal contaminated waters using redox-sensitive iron nanoparticle-loaded biochar.

The unceasing release of tiny plastics (microplastics and nanoplastics) and their additives, like metal ions, into the aquatic systems from industries and other sources is a globally escalating problem. Their combined toxic effects and human health hazard are already proven; hence, their remediation is requisite. This study utilised the nano-zerovalent iron-loaded sugarcane bagasse-derived biochar (nZVI-SBC) for simultaneous removal of Nanoplastics (NPs) of different functionality and size along with metal ions (Ni2+, Cd2+, AsO43-, and CrO42-). Batch and column experiments were conducted, and the results showed an efficient removal of contaminants with maximum sorption of carboxylate-modified NPs of size 500 nm (qmax = 90.3 mg/g) among all three NPs types. Significant removal was observed in Cd2+ in case of cations and CrO42- in case of anions with qmax = 44.0 and 87.8 mg/g, respectively. Kinetics and the isotherm modelling better fitted the pseudo-second-order kinetic model and Sips isotherm model, respectively for both NPs and metal ions. The designed material worked well in pH range of 4-8, ionic strength 1-20 mM and in complex aqueous matrices, with >90% removal. FTIR, zeta potential and the imaging analysis of the reaction precipitates confirmed the electrostatic attraction, pore retention and complexation as the potential mechanisms for removing NPs, whereas, XPS studies confirmed the reduction co-precipitation and surface complexation as the possible mechanism for removing metal ions. High values of attachment efficiency factor calculated from colloidal filtration theory (CFT) validated the experimental results and justified the high sorption of carboxylate modified 500 nm NPs particles. The synthesized material successfully removed both NPs of varying size and functionality and metal ions simultaneously with significant efficacy in complex environmental samples proving the broad applicability of material in realistic environmental conditions and different types of water treatment processes.