nZVI Particles Research Articles

Catalytic ozone pretreatment of complex textile effluent using Fe2+ and zero valent iron nanoparticles

The study investigates the effect of catalytic ozone pretreatment via Fe2+ and nZVI on biodegradability enhancement of complex textile effluent. The nZVI particles were synthesized and characterized by XRD, TEM and SEM analyses. Results showed that nano catalytic ozone pretreatment led to higher biodegradability index (BOD5/COD = BI) enhancement up to 0.61 (134.6%) along with COD, color and toxicity removal up to 73.5%, 87%, and 92% respectively. The disappearance of the corresponding GCMS & FTIR spectral peaks during catalyzed ozonation process indicated the cleavage of chromophore group and degradation of organic compounds present in the textile effluent. Subsequent aerobic biodegradation of nZVI pretreated textile effluent resulted in maximum COD and color reduction of 78% and 98.5% respectively, whereas the untreated effluent (BI = 0.26) indicated poor COD and color reduction of only 31% and 33% respectively. Bio-kinetic parameters also confirmed the increased rate of bio-oxidation at enhanced BIs. Seed germination test using seeds of Spinach (Spinacia oleracea), indicated the effectiveness of nano catalyzed ozone pretreatment in removing toxicity from contaminated textile effluent.

Nanoscale Zero-Valent Iron Decorated on Bentonite/Graphene Oxide for Removal of Copper Ions from Aqueous Solution.

The removal efficiency of Cu(II) in aqueous solution by bentonite, graphene oxide (GO), and nanoscale iron decorated on bentonite (B-nZVI) and nanoscale iron decorated on bentonite/graphene oxide (GO-B-nZVI) was investigated. The results indicated that GO-B-nZVI had the best removal efficiency in different experimental environments (with time, pH, concentration of copper ions, and temperature). For 16 hours, the removal efficiency of copper ions was 82% in GO-B-nZVI, however, it was 71% in B-nZVI, 26% in bentonite, and 18% in GO. Bentonite, GO, B-nZVI, and GO-B-nZVI showed an increased removal efficiency of copper ions with the increase of pH under a certain pH range. The removal efficiency of copper ions by GO-B-nZVI first increased and then fluctuated slightly with the increase of temperature, while B-nZVI and bentonite increased and GO decreased slightly with the increase of temperature. Lorentz-Transmission Electron Microscope (TEM) images showed the nZVI particles of GO-B-nZVI dispersed evenly with diameters ranging from 10 to 86.93 nm. Scanning electron microscope (SEM) images indicated that the nanoscale iron particles were dispersed evenly on bentonite and GO with no obvious agglomeration. The qe,cal (73.37 mg·g−1 and 83.89 mg·g−1) was closer to the experimental value qe,exp according to the pseudo-second-order kinetic model. The qm of B-nZVI and GO-B-nZVI were 130.7 mg·g−1 and 184.5 mg·g−1 according to the Langmuir model.

Calcium hydroxide coating on highly reactive nanoscale zero-valent iron for in situ remediation application

Nano scale zero-valent iron (nZVI), a promising engineering technology for in situ remediation, has been greatly limited by quick self-corrosion and low mobility in porous media. Highly reactive nZVI particles produced from the borohydride reduction method were enclosed in a releasable Ca(OH)2 layer by the chemical deposition method. The amount of Ca(OH)2 coated on nZVI surface were well controlled by the precursor dosage. At moderate Ca(OH)2 dosage (RCa/TFe = 0.25) condition, the increment of Fe0 content for the obtained nZVI/Ca-0.25 sample was observed. The interfacial reactions between the iron oxide shell and the Ca(OH)2 saturated environment were delicately elucidated by the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) spectrum. And the coverage of Ca(OH)2 shell on spherical nZVI surface was found more complete and uniform for the nZVI/Ca sample obtained from the moderate precursor dosage condition (RCa/TFe = 0.25). The Ca(OH)2 shell before dissolution was demonstrated owning the anti-corrosion capability to slow down the oxidation of Fe0 core in air, during ethanol storage and in aqueous environment. The mechanism of anti-corrosion capability for nZVI/Ca-0.25 particle was interestingly found to be attributed to the Ca(OH)2 shell isolation and also be potentially due to the iron oxide shell phase transformation mediated by the outer Ca(OH)2 shell. An improved trichloroethylene reduction performance was observed for nZVI/Ca-0.25 than bare nZVI. The mobility of nZVI/Ca particles in water-saturated porous media was moderately improved before shell dissolution.

Using Silica Coated Nanoscale Zerovalent Particles for the Reduction of Chlorinated Ethylenes

The impact of a silica coating on the degradation potential of nanoscale zerovalent iron (nZVI) particles toward a mixture of chlorinated ethylenes is presented. The newly employed stabilization method for nZVI, based on silica deposition from saturated sodium silicate water glass, produces nZVI particles with a similar reactivity as non-stabilized particles. Moreover the removal rate constant kM of trichloroethylene (0.1740 L g−1 d−1 Fe0) and cis-dichloroethylene (0.1045 L g−1 d−1Fe0) was significantly improved (almost by a factor of 2) for stabilized nZVI. X-ray photoelectron spectroscopy (XPS) and Wavelength Dispersive X-ray Fluorescence (WDXRF) analyzes revealed a high durability of silica coating and the coating left at least half of nZVI surface silica free for reaction for more than 5 weeks. The silica coating did not affect the surface composition of silica coated nZVI which was confirmed by the very similar distribution of degradation products and corrosion products (Fe3O4, FeOOH) as was found for non-coated nanoparticles. An enhanced reactivity supplemented with a stable corrosion properties indicates that silica coated nZVI has potential as an efficient remediation agent toward chlorinated ethylenes.

Nanoscopic Zero-Valent Iron Supported on MgO for Lead Removal from Waters

Lead is one of the most toxic heavy metals that can create a severe risk to water ecosystem health. Zero-valent iron is an effective material for Pb2+ removal treatments. In particular, nanoscopic zero-valent iron (nZVI) particles are characterized by high reaction rates; nevertheless, their utilization in water and groundwater remediation techniques requires further investigations. Indeed, it is necessary to define effective methods able to avoid the drawbacks due to the aggregation tendency of nanoparticles and their potential uncontrolled transport in groundwater. In this work, nZVI was supported on magnesium oxide grains (MgO_nZVI) to synthesize an alternative material for lead removal from aqueous solutions. Many experiments were conducted under several operating conditions in order to analyze the effectiveness of the produced material in Pb2+ abatement. The performance of MgO_nZVI was also compared with those detected using commercial microscopic Fe0 (mZVI) as a reactive material. The experimental findings showed a much greater reactivity of the supported nanoscopic iron particles. By means of a kinetic analysis of batch tests results, it was verified that, both for MgO_nZVI and mZVI, the lead abatement follows a pseudo-second-order kinetic law. The reaction rates were affected by the initial pH of the treatment solution and by the ratio between the Fe0 amount and initial lead concentration. The efficiency of MgO_nZVI in a continuous test was steadily around 97.5% for about 1000 exchanged pore volumes (PV) of reactive material, while by using mZVI, the lead removal was approximately 88% for about 600 PV. X-ray diffraction (XRD) and energy-dispersive spectroscopy EDS analyses suggested the formation of typical iron corrosion products and the presence of metallic lead Pb0 and Pb2+ compounds on exhausted materials.

Sorption and fractionation of rare earth element ions onto nanoscale zerovalent iron particles

The removal behaviour of rare earth element (REE), (Sc, Y, La-Lu), ions onto nanoscale zerovalent iron (nZVI) particles has been investigated. Batch sorption isotherms were conducted using REE-bearing acid mine drainage (AMD) and a range of different synthetic REE solutions, which were exposed to nZVI at 0.1–4.0 g/L. Maximum adsorption capacity of Yb and La was 410 and 61 mg/g respectively (1000 mg/L LaCl3 and YbCl3 starting concentration, initial pH = 4.5, T = 294 K), the highest currently reported in the literature. Aqueous REE removal to ultratrace concentrations (<1 µg/L, >99.9% removal) was also recorded after 30 min (the first sampling interval) exposure of ≥0.5 g/L nZVI to 10 mg/L aqueous REE solutions (nitrate counterion). Similar rapidity and near-total removal ability was recorded for the exposure of nZVI to the AMD, however, a greater nZVI concentration was required, with the removal of all REEs (with the exception of La, Ce, Nd and Gd) to <1 µg/L when exposed to nZVI at 4.0 g/L for 30 min. In all systems nZVI was selective for the removal of HREE ions in preference to LREE ions, with the mechanism determined using HRTEM-EDS and XPS analysis as via surface mediated precipitation. Overall the results demonstrate nZVI as exhibiting great promise as an effective and versatile agent for simultaneous REE ion recovery and fractionation.

Nanomaterials application for heavy metals recovery from polluted water: The combination of nano zero-valent iron and carbon nanotubes. Competitive adsorption non-linear modeling

Carbon Nanotubes (CNTs) and nano Zero-Valent Iron (nZVI) particles, as well as two nanocomposites based on these novel nanomaterials, were employed as nano-adsorbents for the removal of hexavalent chromium, selenium and cobalt, from aqueous solutions. Nanomaterials characterization included the determination of their point of zero charge and particle size distribution. CNTs were further analyzed using scanning electron microscopy, thermogravimetric analysis and Raman spectroscopy to determine their morphology and structural properties. Batch experiments were carried out to investigate the removal efficiency and the possible competitive interactions among metal ions. Adsorption was found to be the main removal mechanism, except for Cr(VI) treatment by nZVI, where reduction was the predominant mechanism. The removal efficiency was estimated in decreasing order as CNTs-nZVI > nZVI > CNTs > CNTs-nZVI* independently upon the tested heavy metal. In the case of competitive adsorption, Cr(VI) exhibited the highest affinity for every adsorbent. The preferable Cr(VI) removal was also observed using binary systems of the tested metals by means of the CNTs-nZVI nanocomposite. Single species adsorption was better described by the non-linear Sips model, whilst competitive adsorption followed the modified Langmuir model. The CNTs-nZVI nanocomposite was tested for its reusability, and showed high adsorption efficiency (the qmax values decreased less than 50% with respect to the first use) even after three cycles of use.

Nanoscale zero-valent iron@mesoporous hydrated silica core-shell particles with enhanced dispersibility, transportability and degradation of chlorinated aliphatic hydrocarbons

Nanoscale zero-valent iron@mesoporous hydrated silica core-shell particles (NZVI@mHS CSP) with improved dispersibility, transportability and dechlorination strength were successfully synthesized and tested for the removal of chlorinated aliphatic hydrocarbons from groundwater. The structural, electronic and textural features of the NZVI@mHS CSP were characterized by different techniques. The NZVI@mHS CSP depicted a specific surface area of 71 m2·g−1, significantly higher, compare to NZVI (12 m2·g−1), with a mesoporous network due to the formation of a hydrated silica shell surrounding the NZVI particle. NZVI@mHS CSP showed an enhanced transportability in sand column compared with NZVI, related to the suspension stability, small aggregated particle size (<1.3 μm) and negative particle charge (−12.11 mV) at neutral pH. NZVI@mHS CSP achieved higher degradation rates than NZVI for the dechlorination of 1,1,1-TCA in synthetic solution and CAHs in real groundwater samples. The dechlorination pathway of 1,1,1-trichloroethane was studied in detail, revealing the formation of 1,1-dichloroethane, ethylene and ethane as the main products. The results of this study prove the ability of NZVI@mHS CSP to transport through a sand column and degrade CAHs pollutants present in real groundwater.

Enhanced reactivity of nZVI embedded into supermacroporous cryogels for highly efficient Cr(VI) and total Cr removal from aqueous solution

Novel supermacroporous PSA-nZVI composites with nanoscale zero-valent iron particles (nZVI) embedded into poly (sodium acrylate) (PSA) cryogels were synthesized through ion exchange followed by in-situ reduction. The magnetic composites were evaluated for material characterizations and their efficiency for Cr(VI) and total Cr removal from aqueous medium in batch experiments. PSA-nZVI composites with high nZVI loading capacity up to 128.70 mg Fe/g PSA were obtained, and the interconnected macroporous structure of PSA cryogel remained unaltered with nZVI uniformly distributed on PSA cryogel as determined by TGA, SEM, TEM, XRD and XPS analyses. PSA-nZVI composites showed faster reaction rate than free nZVI both for Cr(VI) and total Cr removal, suggesting no mass transfer resistance and the enhanced reactivity of nZVI in PSA carrier. PSA-nZVI composites exhibited much more remarkable performance for Cr(VI) and total Cr removal than free nZVI particles in high removal capacity and broad pH application range (pH 4–10). The reaction mechanisms were also elucidated with XPS analyses before and after Cr(VI) reduction reactions. These results demonstrate that PSA cryogel acts as an excellent carrier and shows multiple functions in nZVI particle dispersion, pH buffering and oxidation resistance in addition to immobilizing nZVI particles from release.

Wastewater degradation by iron/copper nanoparticles and the microorganism growth rate

Nowadays, trends in wastewater treatment by zero-valent iron (ZVI) were turned to use bimetallic NZVI particles by planting another metal onto the ZVI surface to increase its reactivity. Nano size zero-valent iron/copper (NZVI/Cu0) bimetallic particles were synthesized in order to examine its toxicity effects on the wastewater microbial life, kinetics of phosphorus, ammonia stripping and the reduction of chemical oxygen demand (COD). Various concentrations of NZVI/Cu0 and operation conditions both aerobic and anaerobic were investigated and compared with pure NZVI experiment. The results showed that addition 10mg/L of NZVI/Cu0 significantly increased the numbers of bacteria colonies under anaerobic condition, conversely it inhibited bacteria activity with the presence of oxygen. Furthermore, the impact of nanoparticles on ammonia stripping and phosphorus removal was also linked to the emitted iron ions electrons. It was found that dosing high concentration of bimetallic NZVI/Cu0 has a negative effect on ammonia stripping regardless of the aeration condition. In comparison to control, dosing only 10mg/L NZVI/Cu0, the phosphorus removal increased sharply both under aerobic and anaerobic conditions, these outcomes were obtained as a result of complete dissolution of bimetallic nanoparticles which formed copper-iron oxides components that are attributed to increasing the phosphorus adsorption rate.

Modification, characterization and investigations of key factors controlling the transport of modified nano zero-valent iron (nZVI) in porous media

ABSTRACTEnhancement of nano zero-valent iron (nZVI) stability and transport in the subsurface environment is important for in situ degradation of contaminants. Various biodegradable dispersants (poly (acrylic acid) (PAA), Tween 20 and Reetha Extracts) have been tested to evaluate their effectiveness in this regard. Application of dispersants during the synthesis of nZVI have positively affected the reduction in particle size. The transport capacity in terms of fraction elution at different pore water velocities and collector grain size (filter media) was analyzed using correlation equation for the filtration model by Rajagopalan and Tien (RT model). At a surfactant concentration of 5% for PAA, Tween 20 and Reetha (Sapindus trifoliata) extracts, the lowest particle size and the highest zeta potential achieved are 8.67 nm and −55.29 mV, 75.24 nm and −62.68 mV, 61.6 nm and −37.82 mV, respectively. The trend of colloidal stability by The Derjaguin—Landau—Verwey—Overbeek (DLVO) Theory model for PAA and Reetha applied concentration was 3% > 4% > 5% > 2% > 1% > 0%. For Tween 20, modified nZVI particle shows a higher repulsive force with increasing Tween 20 concentration. Results indicated that some mechanisms such as aggregation, ripening and surface modification with different carrier pore water velocities had a considerable impact on nZVI retention in porous media. The results indicate that natural surfactant like Reetha extracts exhibits an alternative potential capacity for nZVI modification in comparison with synthetic surfactants (PAA and Tween 20).

Nitrobenzene reduction using nanoscale zero-valent iron supported by polystyrene microspheres with different surface functional groups.

Three polystyrene (PS) resin microspheres supported nanoscale zero-valent iron (nZVI), i.e., nZVI@PS, nZVI@PS-Cl, and nZVI@PS-N, were prepared and characterized by FT-IR, XPS, SEM, EDS, and weighing method. The functional groups on the carriers showed obvious influence on the loading quantity, the micro morphology, and the reduction efficiency of these supported nZVI. The best hybrid reducer was nZVI@PS-N. The load quantity of nZVI was 0.2476g/g, and some of them were dispersed and the others remained as particles (≤ 50nm). At optimal reaction conditions, i.e., initial solution pH = 3, 25°C, 100r/min stirring, 99% nitrobenzene (NB) in 250mL 123.1mg/L NB solution could be totally reduced into AN by 1.31g fresh nZVI@PS-N within 20min. The excellent reduction efficiency and fast degradation rate of nZVI@PS-N were mainly attributed to the synergistic effects between the good adsorption property of its carrier and the high reduction activity of nZVI particles. NZVI@PS-N was reproducible and recycled, and 90.6% degradation ratio of NB was till obtained at its seventh recycle. The results showed that nZVI@PS-N had high potential practical application value in the reductive degradation and emergency rescue of nitrobenzene pollutant.

Removal of Trinitrotoluene with Nano Zerovalent Iron Impregnated Graphene Oxide

Nano zerovalent iron (nZVI) impregnated reduced graphene oxide (nZVI-rGO) hybrid was prepared via gaseous hydrogen reduction of anhydrous iron(III) chloride (FeCl3) on the surface of thermally exfoliated reduced graphene oxide (rGO) nanosheets without using any toxic reducing agent, surfactant, or stabilizing agent. Characterization of prepared samples was carried out using various techniques. Morphological study showed that prepared rGO possesses a few-layered wrinkled paper-like structures and nZVI particles of ~ 30 nm size were homogeneously dispersed on the surface of rGO nanosheets. Fourier transform infrared (FTIR), X-ray diffraction (XRD), and energy dispersive X-ray spectrometry (EDS) analyses indicated that oxygen-containing functional groups decreased in the order of graphite oxide (GO) > rGO > nZVI-rGO. Removal studies of trinitrotoluene (TNT) were carried out using graphite (G), GO, rGO, and nZVI-rGO with the aid of high-performance liquid chromatography (HPLC). Kinetic models were applied to establish the rate and mechanism of adsorption of TNT on different adsorbents, and intraparticle diffusion model based on initial adsorption characteristics was employed to ascertain mechanism of film and intraparticle diffusion in the adsorption process. The removal rate and adsorption capacity was found to be highest for nZVI-rGO, which renders this adsorbent to be a potential futuristic adsorbent for removal of explosives.

Mapping the Reactions in a Single Zero-Valent Iron Nanoparticle.

Nanoscale zerovalent iron (nZVI) possesses unique functionalities for metal-metalloid removal and sequestration. So far, direct evidence on the heavy metal-nZVI reactions in the solid phase is still limited due to low concentration of heavy metals and small size of nanoparticles. In this work, angstrom-resolution spectral mappings on the reactions of nZVI with chromate, arsenate, nickel, silver, cesium, and zinc ions are presented. This work was achieved with spherical aberration-corrected scanning transmission electron microscopy integrated with high-sensitivity X-ray energy-dispersive spectroscopy-scanning transmission electron microscopy (XEDS-STEM). Results confirm that iron nanoparticles have a core-shell structure. In addition, the removal mechanism significantly depends on the standard potential E0 (E0 is standard potential w.r.t. standard hydrogen electrode at 25 °C when free ion activity is 1.). For strong oxidizing agents, such as Cr(VI), the removal mechanism is diffusion and encapsulation in the core area of the nZVI particle. For moderate oxidizers, such as As(V) with E0 more positive than that of iron, the removal mechanism is adsorption at the surface, followed by diffusion and encapsulation into the particle between the core and the shell. For metal cations with an E0 close to or more negative than that of iron, such as Cs(I) and Zn(II), the removal mechanism is sorption or surface-complex formation. For metal cations with E0 much more positive than that of iron, such as Ag(I), the removal mechanism is rapid reduction on the surface of nZVI. Meanwhile, metals with E0 slightly more positive than that of iron, such as Ni(II), can be immobilized at the nanoparticle surface via sorption and reduction. The synergetic effects of sorption, reduction, and encapsulation mechanisms of nZVI lead to rapid reactions and high efficiency for treatment and immobilization of many toxic heavy metals. Results also demonstrate that the XEDS-STEM technique is a powerful tool for studying reactions in individual nanoparticles and is particularly valuable for mapping trace-level elements in environmental media.

Chemical reduction of nitrate by zerovalent iron nanoparticles adsorbed radiation-grafted copolymer matrix

Abstract This research specifically focused on the development of a novel methodology to reduce excess nitrate in drinking water utilizing zerovalent iron nanoparticles (nZVI)-stabilized radiation-grafted copolymer matrix. nZVI was synthesized by borohydrate reduction of FeCl3 and stabilized on acrylic acid (AAc)-grafted non-woven polyethylene/polypropylene (NWPE/PP-g-AAc) copolymer matrix, which was grafted using gamma radiation. The use of nZVI for environmental applications is challenging because of the formation of an oxide layer rapidly in the presence of oxygen. Therefore, radiation-grafted NWPE/PP synthetic fabric was used as the functional carrier to anchor nZVI and enhance its spreading and stability. The chemical reduction of nitrate by nZVI-adsorbed NWPE/PP-g-AAc (nZVI-Ads-NWP) fabric was examined in batch experiments at different pH values. At low pH values, the protective layers on nZVI particles can be readily dissolved, exposing the pure iron particles for efficient chemical reduction of nitrate. After about 24 h, at pH 3, almost 96% of nitrate was degraded, suggesting that this reduction process is an acid-driven, surface-mediated process. The nZVI-water interface has been characterized by the 1-pK Basic Stern Model (BSM). An Eley-Rideal like mechanism well described the nitrate reduction kinetics. In accordance with green technology, the newly synthesized nZVI-Ads-NWP has great potential for improving nitrate reduction processes required for the drinking water industry.

Degradation of Carbon Tetrachloride by nanoscale Zero‐Valent Iron @ magnetic Fe3O4: Impact of reaction condition, Kinetics, Thermodynamics and Mechanism

Nano‐scale zero‐valent Iron (nZVI) attached on the Fe3O4 nanoparticles were prepared and creatively applied in the reductive dechlorination of Carbon Tetrachloride (CT). The characterization results of the synthesized composite indicated a main component of nZVI particles assembled on the surface of Fe3O4 with a layer of iron‐oxide film on the periphery, of which the dispersibility was better and the specific surface area was larger. The effects of different reaction conditions like temperature, initial pH values, Fe0@Fe3O4 dosage and initial CT concentrations on the removal of CT were evaluated. Under the optimum conditions, the Fe0@Fe3O4 composites showed a CT removal efficiency of 89.1% in 60 min, which was much greater than that of nZVI (61.7%) and Fe3O4 particles (14.3%). The removal process obeyed the pseudo‐first‐order kinetic model. Synergy effects of the constituents in the composite which can promote the relative rates of mass transfer to reactive sites were proposed to be existed and the magnetism of Fe3O4 could help to overcome the aggregation and surface passivation problem of nZVI. Thus, Fe0@Fe3O4 nanoparticles in our study can effectively complete the reductive dechlorination of CT and an improved nZVI catalyst is provided for the remediation of chlorinated organic compounds.

Impact of zero-valent iron nanoparticles on the activity of anaerobic granular sludge: From macroscopic to microcosmic investigation

The study aimed at evaluating the influence of nano zero-valent iron (nZVI) on the activity of anaerobic granular sludge (AGS) from both macroscopic and microcosmic aspects using different methodologies. The tolerance response of AGS to nZVI was firstly investigated using short-term and long-term experiments, and also compared with anaerobic flocs. The Fe fate and distribution, the change of contents/structure of extracellular polymeric substances (EPS), and the variation of microbial community in the AGS after exposure to nZVI were further explored. Contrary to the anaerobic floc, insignificant inhibition of nZVI at dosage lower than 30 mmoL/L on the activity of AGS was observed. Additionally, the extra hydrogen gas released from the oxidation of nZVI was presumably suggested to stimulate the hydrogenotrophic methanogenesis process, resulting in 30% methane production enhancement when exposure to 30 mmoL/L nZVI. The microscopic analysis indicated that nZVI particles were mainly adsorbed on the surface of AGS in the form of iron oxides aggregation without entering into the interior of the granule, protecting most cells from contact damage. Moreover, surrounded EPS located outer surface of anaerobic granule could react with nZVI to accelerate the corrosion of nZVI and slow down H2 release from nZVI dissolution, thus further weakening the toxicity of nZVI to anaerobic microorganisms. The decrease in bacteria involved in glucose degradation and aceticlastic methanogens as well as the increase of hydrogenotrophic methanogens indicated a H2 mediated shift toward the hydrogenotrophic pathway enhancing the CH4 production.

Lead removal by a reusable gel cation exchange resin containing nano-scale zero valent iron

The practical applications of nano-scale zero valent iron (nZVI) particles in flow-through treatment systems are limited due to unfavorable mechanical and hydraulic properties caused by their tiny size. On the other hand, nZVI, when dispersed within suitable host material, can overcome these limitations to have synergistic improvement in its adsorption capacity. This study aims to synthesize, characterize, validate the performance of hybrid cation gel exchanger dispersed with nZVI particles, named as C100-Fe0, for selective trace Pb(II) removal from contaminated water. C100-Fe0 had Fe content of approximately 22% w/w as determined by double acid digestion method. The characterization studies revealed that nZVI particles of size range 20nm were well dispersed throughout the gel phase of the polymeric resin beads; XANES spectral analysis confirmed the presence of zero oxidation state of Fe nanoparticles within both the newly synthesized and regenerated C100-Fe0. Equilibrium batch studies demonstrated that Pb(II) adsorption capacity was unaffected by the presence of high concentration of competing ions such as Na+ and Ca2+ ions whereas, presence of SiO2 decreased the capacity. The batch adsorption isotherm fitted well with Freundlich model. During column study with C100-Fe0, breakthrough of USEPA permissible limit of 15µg/L was observed after the passage of 4200 bed volumes of challenge water (NSF/ANSI Std.53) having Pb(II) concentration of 150µg/L. More than 87% of adsorbed Pb (II) could be recovered within 15 bed volumes during regeneration with acid. Wide availability and low price of iron salts as well as of cation exchange resins, combined with the possible reusability make C100-Fe0 an attractive option for use in the field for removal of Pb(II) from contaminated water.

Mapping fracture flow paths with a nanoscale zero-valent iron tracer test and a flowmeter test

The detection of preferential flow paths and the characterization of their hydraulic properties are important for the development of hydrogeological conceptual models in fractured-rock aquifers. In this study, nanoscale zero-valent iron (nZVI) particles were used as tracers to characterize fracture connectivity between two boreholes in fractured rock. A magnet array was installed vertically in the observation well to attract arriving nZVI particles and identify the location of the incoming tracer. Heat-pulse flowmeter tests were conducted to delineate the permeable fractures in the two wells for the design of the tracer test. The nZVI slurry was released in the screened injection well. The arrival of the slurry in the observation well was detected by an increase in electrical conductivity, while the depth of the connected fracture was identified by the distribution of nZVI particles attracted to the magnet array. The position where the maximum weight of attracted nZVI particles was observed coincides with the depth of a permeable fracture zone delineated by the heat-pulse flowmeter. In addition, a saline tracer test produced comparable results with the nZVI tracer test. Numerical simulation was performed using MODFLOW with MT3DMS to estimate the hydraulic properties of the connected fracture zones between the two wells. The study results indicate that the nZVI particle could be a promising tracer for the characterization of flow paths in fractured rock.

“Robbing behavior” and re-immobilization of nanoscale zero-valent iron (nZVI) onto electrospun polymeric nanofiber mats for trichloroethylene (TCE) remediation

Abstract In this study, we first revealed a “robbing behavior” during the immobilization of nZVI particles onto an electrospun polyacrylic acid (PAA)-polyvinyl alcohol (PVA) nanofiber mat. The robbing behavior can significantly reduce the number of nZVI particles immobilized onto the mat and hence weaken the performance of mitigating contaminated water. To minimize the undesirable effect of robbing behavior, we developed a dipping method that enables exposure of enough free Fe (II) as electron acceptors to the Fe (II)-complexed PAA-PVA mat for the subsequent reduction. The result indicates that the mat with dipping can immobilize more than 1.7 times the weight percentage of nZVI particles for the mat without dipping. Moreover, the dipping method can also re-immobilize or enrich nZVI particles on the mat that has already partially immobilized nZVI particles. The nZVI-immobilized mat dipped once into the FeSO4 solution with a very little concentration (0.32 g/L) had an excellent performance for trichloroethylene (TCE) degradation (more than 92% TCE removed). Here, the developed dipping method shows great potential for nZVI immobilization and groundwater remediation.