Zero-valent Iron Particles Research Articles

Effective treatment of 2,4,6-trinitrotoluene from aqueous media using a sono-photo-Fenton-like process with a zero-valent iron nanoparticle (nZVI) catalyst.

In this study, we examine the effectiveness of using a combination of a sono-photo-Fenton-like procedure and nano zero-valent iron catalyst (nZVI) to treat 2,4,6-trinitrotoluene (TNT) in an aquatic environment. Zero-valent iron particles were generated by a chemical reduction technique. nZVI nanoparticles were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD) to characterize the nanocatalyst. The resulting nZVI nanoparticles were used as an addition in a sono-photo-Fenton method to remediate an aqueous solution contaminated with TNT. Furthermore, influences of operational factors such as temperature, catalyst dosage, wavelength, ultraviolet power, ultrasonic frequency and power, pH level, H2O2/nZVI ratio, initial TNT concentration, and reaction duration on the treatment of TNT were investigated. Under the conditions of an ideal pH of 3, temperature range of 40-45 °C, concentration of 50 mg per L TNT, dose of 2 mM of nZVI, and ratio of H2O2/Fe0 of 20, a treatment efficiency of 95.2% was achieved after a duration of 30 minutes. The sono-photo-Fenton process combined with nZVI showed a higher TNT removal efficiency compared to the Fenton, sono-Fenton, and photo-Fenton processes under the same conditions. Moreover, it promises a potential solution to treat TNT at the pilot scale while allowing reuse of the nZVI catalyst and the limitation of sludge.

Accelerated Iron Corrosion by Microbial Consortia Enriched from Slime-like Precipitates from a Corroded Metal Apparatus Deployed in a Deep-sea Hydrothermal System.

Microbiologically influenced corrosion refers to the corrosion of metal materials caused or promoted by microorganisms. Although some novel iron-corrosive microorganisms have been discovered in various manmade and natural freshwater and seawater environments, microbiologically influenced corrosion in the deep sea has not been investigated in detail. In the present study, we collected slime-like precipitates composed of corrosion products and microbial communities from a geochemical reactor set on an artificial hydrothermal vent for 14.5 months, and conducted culture-dependent and -independent microbial community ana-lyses with corrosive activity measurements. After enrichment cultivation at 37, 50, and 70°C with zero-valent iron particles, some of the microbial consortia showed accelerated iron dissolution, which was approximately 10- to 50-fold higher than that of the abiotic control. In a comparative ana-lysis based on the corrosion acceleration ratio and amplicon sequencing of the 16S rRNA gene, three types of corrosion were estimated: the methanogen-induced type, methanogen-sulfate-reducing bacteria cooperative type, and sulfate-reducing Firmicutes-induced type. The methanogen-induced and methanogen-sulfate-reducing bacteria cooperative types were observed at 50°C, while the sulfate-reducing Firmicutes-induced type was noted at 37°C. The present results suggest the microbial components associated with microbiologically influenced corrosion in deep-sea hydrothermal systems, providing important insights for the development of future deep-sea resources with metal infrastructures.

Influence of pyrite on oxidative treatment of diclofenac with zero-valent iron/H2O2 system coupled with chemical precipitation under controlled and uncontrolled pH conditions

Batch experiments, combined with surface measurements, were conducted to elucidate the impact of pyrite on diclofenac treatment by zero-valent iron (ZVI)/H2O2 system. In binary systems with ZVI/H2O2, diclofenac removal was limited under controlled-pH conditions due to the agglomeration of ZVI particles and low rate of iron leaching. However, the use of pyrite in batch systems under uncontrolled-pH conditions drastically increased diclofenac removal by the ZVI/H2O2 system due to a significant drop in pH and enhanced iron dissolution. The diclofenac removal by the ternary ZVI/pyrite/H2O2 system could be explained through a combined effect of adsorption, oxidative degradation of diclofenac with hydroxyl radicals (*OH) and chemical precipitation of diclofenac and/or its intermediate species with the iron species dissolved from the ZVI/pyrite particles. While adsorption/chemical precipitation accounted for 75% of diclofenac removal in the initial stage, oxidative degradation achieved the remaining 25% diclofenac removal in the second stage. Surface analyses show that, in systems with diclofenac, the iron species dissolved from ZVI and pyrite particles complexed with diclofenac and/or intermediate species to form some spherical particles. Overall, this study sheds light on the reaction mechanism for the practical application of the ternary ZVI/pyrite/H2O2 system to diclofenac removal.

Synthesis of stabilized zero-valent iron particles and role investigation of humic acid-Fex+ shell in Fenton-like reactions and surface stability control

Herein, a novel humic acid-Fex+ complex-coated ZVI (HA-Fex+@ZVI) was synthesized and used to activate peroxydisulfate (PDS) for phenol degradation. The HA-Fex+ shell selectively reacted with PDS rather than O2, leading to the formation of modified ZVI with excellent surface stability in storage and ultraefficient PDS activation in advanced oxidation processes (AOPs). As a result, the phenol degradation and PDS activation efficiencies of HA-Fex+@ZVI/PDS were ∼14.4 and ∼1.8 times higher than those of ZVI/PDS, respectively. Mechanistic explorations revealed that the replacement of the HA-Fex+ shell relative to the original passivation layer of ZVI greatly changed the SO4•- generation pathway from a heterogeneous process to a homogeneous process, resulting from the slow exposure of Fe0 (generating dissolved Fe2+) and the depolymerized HA (enhancing the Fe3+/Fe2+ cycle). Based on experimental analysis and density functional theory (DFT) calculations, the Fe3+ in HA-Fex+ could be reduced to Fe2+ by PDS, resulting in the disintegration of the HA-Fex+ shell and exposure of Fe0 core active sites. Furthermore, compared to similar catalysts synthesized with commercial HA and traditional chemicals, HA-Fex+@ZVI synthesized with multiple waste biomasses exhibited better performance. This research provides valuable insights for designing ZVI-based catalysts with excellent storage stability and ultraefficient PDS catalytic activity for AOPs.

Study on tetracycline degradation in wastewater based on zero-valent nano iron assisted micro-nano bubbles

The presence of antibiotics in wastewater has become a significant concern due to their potential environmental impact and contribution to antibiotic resistance. In this study, we investigated the degradation of tetracycline, a commonly used antibiotic, in wastewater using a system based on zero-valent nano iron assisted micro-nano bubbles (MB/nZVI). The synthesized nZVI-BC composite, consisting of nano zero-valent iron particles loaded onto phosphoric acid-activated biochar, served as an efficient adsorbent for tetracycline removal. Our findings revealed that the combination of MBs and nZVI significantly enhanced the degradation efficiency of tetracycline. The MB/nZVI system exhibited the highest removal rate of 82.81% after a 2 h reaction, surpassing the performance of MB alone, nZVI-BC alone, and conventional bubble (CB)/nZVI-BC systems. Furthermore, the MB/nZVI system showed superior degradation performance at a dosage of 25 g/L and an MB flow rate of 30 mL/min. The pH condition had no significant effect on tetracycline degradation in the MB/nZVI system. Our results demonstrate that the use of MB/nZVI has the potential to be a sustainable and efficient approach for the remediation of tetracycline-contaminated wastewater.

Promotion of medium-chain fatty acids and long-chain alcohols production by zero-valent iron: Effect of particle sizes

The effect of zero-valent iron (ZVI) particle size on biological chain elongation (CE) was explored. The addition of ZVI particles with diameters of 50 nm-1000 µm stimulated both medium-chain fatty acids (MCFAs) and long-chain alcohols (LCAs) production, and increased carbon conversion rate of CE process by 2.8–12.2 times. ZVI particle size of 75 µm exhibited the best performance in promoting MCFAs production, achieved the highest MCFAs production of 2164.2 mg/L, which was 11.9 times of control group. ZVI particle size of 1000 µm showed the best performance in stimulating LCAs production, obtained the highest LCAs production of 434.0 mg/L, which was 33.4 times of the control group. Microbial community analysis suggested that different ZVI particle sizes significantly affected genus Clostridium_sensu_stricto_12 and Clostridium_sensu_stricto_7. Functional enzyme analysis revealed that 75 µm ZVI particles induced the strengthened reverse β oxidation pathway, while 1000 µm ZVI particles enhanced the fatty acid biosynthesis pathway.

Enhanced electron transfer pathway of zero-valent iron particles immobilized on coconut shell derived carbon for prolonged Cr(VI) removal

Immobilizing zero-valent iron (ZVI) with modulated structure and good dispersibility is of great potential for the elimination of Cr(VI) in contaminated water or soil, but exploring how the support facilitate and prolong the removal of Cr(VI) by ZVI in terms of the electron transfer is inadequate. Coconut shell derived carbon could be promising for Cr(VI) removal due to the features of large specific surface area and porosity. Accordingly, ZVI particles are dispersed into low-cost and scalable coconut shell derived carbon (CSC) matrix uniformly in this study, with enhanced contact area and interaction of ZVI with CSC for effective elimination of Cr(VI). The optimal ZVI/CSC-0.65 demonstrates an equilibrium adsorption capacity of 307.8 mg/g and long-life Cr(VI) cleanup ability over 144 h. The interface reaction mechanism between ZVI/CSC and Cr contaminant have been systematically studied by various techniques including XRD, SEM/TEM and XPS, etc. ZVI’s aggregation and passivation in ZVI/CSC-0.65 have been greatly alleviated. Further analysis by Tafel polarization and DFT computation suggests ZVI/CSC-0.65 undergoes fast electron transfer, with a much higher adsorption energy (−2.90 eV) than that of pristine ZVI (−0.63 eV). The Bader charge analysis demonstrates that there is 4.40 |e| charge transferring the ZVI to the carbon, encouraging the Cr(VI) adsorption. A micro-battery based mechanism is proposed which provides an additional electron transfer pathway in ZVI/CSC for long-term Cr(VI) removal.

Incorporation of N-doped biochar into zero-valent iron for efficient reductive degradation of neonicotinoids: mechanism and performance

The extensive use of neonicotinoids on food crops for pest management has resulted in substantial environmental contamination. It is imperative to develop an effective remediation material and technique as well as to determine the evolution pathways of products. Here, novel ball-milled nitrogen-doped biochar (NBC)-modified zero-valent iron (ZVI) composites (named MNBC-ZVI) were fabricated and applied to degrading neonicotinoids. Based on the characterization results, NBC incorporation introduced N-doped sites and new allying heterojunctions and achieved surface charge redistribution, rapid electron transfer, and higher hydrophobicity of ZVI particles. As a result, the interaction between ZVI particles and thiamethoxam (a typical neonicotinoid) was improved, and the adsorption–desorption and reductive degradation of thiamethoxam and ·H generation steps were optimized. MNBC-ZVI could rapidly degrade 100% of 10 mg·L−1 thiamethoxam within 360 min, its reduction rate constant was 12.1-fold greater than that of pristine ZVI, and the electron efficiency increased from 29.7% to 57.8%. This improved reactivity and selectivity resulted from increased electron transfer, enhanced hydrophobicity, and reduced accumulation of iron mud. Moreover, the degradation of neonicotinoids occurred mainly via nitrate reduction and dichlorination, and toxicity tests with degradation intermediates revealed that neonicotinoids undergo rapid detoxification. Remarkably, MNBC-ZVI also presented favorable tolerance to various anions, humic acid, wastewater and contaminated soil, as well as high reusability. This work offers an efficient and economic biochar-ZVI remediation technology for the rapid degradation and detoxification of neonicotinoids, significantly contributes to knowledge on the relevant removal mechanism and further advances the synthesis of highly reactive and environmentally friendly materials.Graphical

Behavior of multi-layer permeable reactive barriers for groundwater remediation

This paper aims to evaluate the efficiency of a multilayer configuration of a permeable reactive barrier (PRB) made up of granular mixtures of zero valent iron (ZVI) and lapillus. The latter is a volcanic material used to disperse ZVI particles. A high dispersion of ZVI improves the long-term hydraulic conductivity but can significantly reduce reactivity due to the lower amount of ZVI. In this research, the performance of two different combinations of a two-layer configuration was studied by means of long-term column tests. The first layer, named “pre-treatment layer”, had a thickness of 4 cm and a volumetric ratio (ZVI/lapillus) of 10:90 or 05:95, while the second layer had a volumetric ratio (ZVI/lapillus) of 20:80. A single layer configuration made only of the 20:80 ZVI/lapillus was used as a benchmark. The three tests were performed using a multi-contaminated solution of copper, nickel and zinc. Test results showed an early loss of the hydraulic conductivity in the single layer configuration and an increase of PRB longevity by 68 % in the presence of the pre-treatment layer. The pre-treatment zone containing 10 % ZVI delayed the clogging phenomenon, while the zone with 5 % ZVI ensured both the correct long-term hydraulic behavior and a removal efficiency higher than 77.6 % for Nickel and 99 % for copper and zinc at 23 cm of thickness for at least two months.

Exploring the Impact of Surface Functionalization on the Reaction, Magnetophoretic, and Collective Transport Behavior of Nanoscale Zerovalent Iron.

This study provides a systematic analysis of the transport and magnetophoretic behavior of nanoscale zerovalent iron (nZVI) particles, both bare and surface functionalized by poly(ethylene glycol) (PEG) and carboxymethyl cellulose (CMC), after undergoing a chemical reaction. Here, a simple and well-investigated chemical reaction of methyl orange (MO) degradation by nZVI was used as a model reaction system, and the sand column transport and low-gradient magnetophoretic profiles of the nanoparticles were measured before and after the reaction. The results were compared over time and analyzed in the context of extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory to understand the particle interactions involved. The colloidal stability of both bare and functionalized nZVI particles was enhanced after the reaction due to the consumption of metallic Fe content, resulting in a significant drop in their magnetic properties. As a result, they exhibited improved mobility across the sand column and a slower magnetophoretic collection rate compared to the unreacted particles. Here, the colloidal filtration theory (CFT) was employed to analyze the transport behavior of nZVI particles across the packed sand column. It has been observed that the surface properties of the reacted functionalized particles changed, possibly due to the entrapment of degraded products within the polymer adlayer. Moreover, quartz crystal microbalance with dissipation (QCM-D) measurements were performed to reveal the viscoelastic contribution of the adlayer formed by both bare and functionalized nZVI particles after the reaction on influencing their transport behavior across the sand column. Finally, we proposed the implementation of a high-gradient magnetic trap (HGMT) to reduce the transport distance of the colloidally stable CMC-nZVI, both before and after the reaction. This study sheds light on the behavioral changes of iron nanoparticles after the reaction and highlights environmental concerns regarding the presence of reacted nanoparticles.

Immobilizing arsenic in contaminated anoxic aquifer sediment using sulfidated and uncoated zero-valent iron (ZVI)

Arsenic (As) is carcinogenic and of major concern in groundwater. We collected sediment material from a contaminated anoxic aquifer in Sweden and investigated the immobilization of As by four commercial zero-valent iron (ZVI) particles. Solid-phase As and Fe speciation was assessed using X-ray absorption spectroscopy (XAS) and solution-phase As speciation using chromatographic separation. Without ZVI addition, arsenite dominated in solution and As(V) species in the solid phase. Adding ZVI caused a sharp increase in solution pH (9.3–9.8), favoring As oxidation despite a lowered redox potential. ZVI greatly improved As retention by complex binding of arsenate to the Fe(III) (hydr)oxides formed by ZVI corrosion. Uncoated ZVI, both in nano- and microscale, performed better than their sulfidated counterparts, partly due to occlusion of As by the Fe(III) (hydr)oxides formed. The effect of particle size (micro vs. nano ZVI) on As immobilization was small, likely because immobilization was related to the corrosion products formed, rather than the initial size of the particles. Our results provide a strong geochemical background for the application of ZVI particles to remove As in contaminated aquifers under anoxic conditions and illustrate that immobilization mechanisms can differ between ZVI in As spiked solutions and sediment suspensions. Environmental implicationArsenic ranks first on the list by the US ATSDR of substances posing a threat to human health and the WHO considers groundwater the riskiest source for human intake of As. However, dealing with As contamination remains a scientific challenge. We studied the immobilization of groundwater As by commercially available ZVI particles at field-realistic conditions. Arsenic immobilization was highly efficient in most cases, and the results suggest this is a promising in situ strategy with long-term performance. Our results provide a strong geochemical background for using ZVI to remove As in contaminated anoxic aquifers.

Sustained activation of persulfate by slow release of Fe(II) from silica-coated nanosized zero-valent iron for in situ chemical oxidation

Sustained activation of persulfate through the slow release of Fe(II) from silica-coated nanosized zero-valent iron (nZVI) particles (nZVI@SiO2) was investigated. Slow release of Fe(II) prevented radical scavenging by excess Fe(II) and increased the radical yield, which improved the stoichiometric efficiency of phenol degradation. Sulfate and hydroxyl radicals were found to be the main oxidative species produced during phenol degradation and were found to make comparable contributions to oxidation. The nZVI@SiO2 particle silica shell thickness controlled the release of Fe(II) and therefore the sustained activation of persulfate and was strongly affected by the synthesis conditions, including the [Si]/[Fe] ratio and silica supply rate. Optimal sustained phenol degradation was achieved when nZVI@SiO2 particles were synthesized using a [Si]/[Fe] ratio of 0.5 and a tetraethyl orthosilicate supply rate of 0.5 mL/min, and this was attributed to the nZVI@SiO2 particles giving an optimal Fe(II) release rate and therefore a high persulfate activation rate and a high phenol removal efficiency. Sustained persulfate activation induced by Fe(II) being slowly released was described well by single-stage first-order kinetics rather than two-stage first-order kinetics typical of unmodified nZVI/persulfate systems. Persulfate was found still to be activated by iron (oxyhydr)oxides minerals after the nZVI@SiO2 particles had been exhausted but the persulfate sustained activation induced by the slow release of Fe(II) played a crucial role in determining the overall degradation efficiency. The results highlight the importance of the slow release of Fe(II) from nZVI-based materials for in situ chemical oxidation through sustained persulfate activation.

Sustainable developmental measures for the treatment of pharmaceutical industry effluent using nano zero valent iron technology (nZVI) – A review

Among the diverse nanomaterials, nanoscale zero-valent iron (nZVI) particle is one of the superior materials used for the condition of remediation and environmental restoration. As a result of the nanoscale dimension of nZVI particles and its relatively high surface, it is capable of undergoing various chemical reactions, including reduction, oxidation and adsorption of toxic metals, inorganic substances and organic compounds. In the pharmaceutical industry, mass production of drugs results in the widespread dumping of effluents. As emerging pollutants, antibiotics are non-biodegradable compounds that have potential to adversely affect human genetic and hormonal systems posing a risk to human health and the environment. Global health is endangered by antibiotics present in surface waters and drinking water. Drug contaminants can be removed using a synergistic process involving various advanced methods, including ozonation, fenton process, photocatalytic degradation, reverse osmosis and, adsorption techniques. The enhancement of nZVI composites and earlier studies were reviewed, as well as the evaluation of zero valent iron nanoparticles' effectiveness in eliminating antibiotic effluents from water bodies. This review also revealed the various methods of the determination of toxicity associated with nZVI treated pharmaceutical effluents. The present study would suggest the possible utilization of nZVI technology for the effective removal of hazardous pharmaceutical contaminants through sustainable green measures.

TEMPO oxidized cellulose nanocrystal (TOCNC) scaffolded nanoscale zero-valent iron (nZVI) for enhanced chromium removal

The conventional carboxymethyl cellulose (CMC) stabilization hampered available active sites of adsorption and reduction, due to irregular shape of nanoscale zero-valent iron (nZVI) particles with augmented average size and passivated surface, leading to insufficient removal and poor resistance against complex environmental conditions. Herein, we presented (2,2,6,6-Tetramethylpiperidine-1-oxyl)-mediated (TEMPO-mediated) oxidation of cellulose nanocrystal (TOCNC) scaffolded nZVI (nZVI@TOCNC) with enhanced efficiency for chromium removal in comparison with CMC stabilized nZVI (nZVI@CMC). The anchoring of nZVI at the functional sites of TOCNC was initiated by liquid-phase chemical reduction method. The nZVI@TOCNC showed improved nZVI distribution with uniform particle size and thinner shell (∼1 nm). Characterizations using FT-IR, XPS and XRD demonstrated that bindings between TOCNC and nZVI were through hydrogen bonds, electrostatic attractions, coordination-covalent bonds and bidentate chelation. TOCNC with shorter branch-chain (–COC–) surrounding the nZVI could potentially form a porous and compact “mesh” to rigidly encapsulate nZVI, while CMC wrapped around nZVI in the way of traditional polymeric stabilizers. Thus, 0.5 g/L nZVI@TOCNC achieved 99.96% Cr (Ⅵ) removal efficiency (20 mg/L) at pH = 7 and the removal capacity were up to 55.86 mg/g. The nZVI@TOCNC consistently presented higher removal efficiency than nZVI@CMC under wide pH range (3–7). Cr (Ⅵ) was reduced to Cr (Ⅲ) by nZVI@TOCNC with deposition of CrxFe1-x (OH)3 and Cr2O3. The predominant mechanisms of removal probably consisted of electrostatic attractions, reduction, co-precipitation and surface complexation. The pseudo-second-order kinetic model well-fitted the sorption kinetic, indicating TOCNC scaffold stabilized nZVI for efficient reduction of Cr (Ⅵ) through multi-layer adsorption. As a template and delivery carrier, TOCNC shows promising potential to further improve the capability and practice of nZVI for in situ treatment of industrial waste water with heavy metal pollution.

Removal of Cr(VI) by glutaraldehyde-crosslinked chitosan encapsulating microscale zero-valent iron: Synthesis, mechanism, and longevity

Microscale zero-valent iron (mZVI) has shown great potential for groundwater Cr(VI) remediation. However, low Cr(VI) removal capacity caused by passivation restricted the wide use of mZVI. We prepared mZVI/GCS by encapsulating mZVI in a porous glutaraldehyde-crosslinked chitosan matrix, and the formation of the passivation layer was alleviated by reducing the contact between zero-valent iron particles. The average pore diameter of mZVI/GCS was 8.775 nm, which confirmed the mesoporous characteristic of this material. Results of batch experiments demonstrated that mZVI/GCS exhibited high Cr(VI) removal efficiency in a wide range of pH (2-10) and temperature (5-35°C). Common groundwater coexisting ions slightly affected mZVI/GCS. The material showed great reusability, and the average Cr(VI) removal efficiency was 90.41% during eight cycles. In this study, we also conducted kinetics and isotherms analysis. Pseudo-second-order model was the most matched kinetics model. The Cr(VI) adsorption process was fitted by both Langmuir and Freundlich isotherms models, and the maximum Langmuir adsorption capacity of mZVI/GCS reached 243.63 mg/g, which is higher than the adsorption capacities of materials reported in most of the previous studies. Notably, the column capacity for Cr(VI) removal of a mZVI/GCS-packed column was 6.4 times higher than that of a mZVI-packed column in a 50-day experiment. Therefore, mZVI/GCS with a porous structure effectively relieved passivation problems of mZVI and showed practical application prospects as groundwater Cr(VI) remediation material with practical application prospects.

Selective removal of Cr(VI) by tannic acid and polyethyleneimine modified zero-valent iron particles with air stability

In this study, a new composite adsorbent for Cr(VI) removal was developed by immobilizing polyethyleneimine (PEI) on the surface of zero-valent iron (ZVI) particles with tannic acid (TA) as a stabilizer. The adsorbent (denoted as Fe-TA-PEI-10) was easy to prepare and regenerate, requiring no conditions for storage. It was found to be particularly effective for Cr(VI) removal from wastewater via reduction and adsorption. Electrochemical analysis revealed that TA significantly reduced the electron transfer resistance of Fe-TA-PEI-10 and reduced the highly toxic Cr(VI)to the less toxic Cr(III). In addition, PEI endowed amino groups to Fe-TA-PEI-10, raising the zero charge point (pHpzc) of Fe-TA-PEI-10 (pHpzc= 7.80), allowing it to adsorb Cr(VI) from the solution rapidly under electrostatic forces and chelating effects. The adsorption process was consistent with the pseudo-first-order model (R2 >0.99) and the Langmuir isotherm model (R2 >0.99), and the maximum adsorption capacity could reach 161.6 mg/g. In particular, this study presented for the first time that TA-modified Fe(0) had excellent stability in the air, and the adsorbent showed no decrease in performance for Cr(VI) removal even after exposure to the air for 30 days. When tested with a simulated electroplating rinsing wastewater, the Fe-TA-PEI-10 showed very high selectivity for Cr(VI) removal. The mechanism of Cr(VI) removal with Fe-TA-PEI-10 was found to be based on adsorption and reduction. This work provided a new scheme for developing efficient and long-lasting reactive adsorbent for Cr(VI) removal.

Stabilization of Iron (0) in plasma treated semi porous polylactic acid based particles for in situ groundwater remediation

This study aims at incorporating reactive zero valent iron (ZVI) nanoparticles into water dispersible, biodegradable polymeric particles acting as a slow release reservoir of ZVI for targeting groundwater contaminants in situ. In order to accomplish the goal, three simple steps were adopted such as: 1) electrojetting of PLA (polylactic acid) with FeCl3 (∼17 wt%) to yield ∼700 nm sized monodisperse spherical particles (PLA_FeCl3) 2) surface modification of PLA_FeCl3 particles using oxygen plasma to enhance surface hydrophilicity and porosity (∼ 75%) 3) reduction of plasma treated PLA_FeCl3 particles in presence of NaBH4 to produce ZVI (size: 20–50 nm) entrapped PLA particles (PLA_ZVI) with high encapsulation efficiency of iron (∼85%). The plasma treated semi-porous PLA_ZVI particles exhibited slow and sustain release of iron (∼90% in ∼100 hrs) that were further employed to completely decontaminate both methyl orange (hydrophilic dye) and trichloroethylene (hydrophobic waste). Interestingly, the plasma treated particles were recyclable up to fourth batch, whereas the non-plasma treated one hardly show any recyclability due to burst release of surface entrapped iron from the latter. Moreover, the plasma treated hydrophilic particles provided stable dispersion (96 hrs) and prolonged reactivity (∼10 days in sand column) in water as opposed to non-plasma treated particles displaying 1 min dispersion stability in water. As a result, the plasma treated particles displayed smooth transportability through sand column (>80%) with negligible attachment efficiency (α = 1.1) onto sand particles. These attributes make them a potential alternative to bare ZVI (transportability <20%) for targeting hazardous pollutants by injecting them in groundwater.

Biogenic ZVI-banana peel activated carbon nanocomposite: Green fabrication and its application for Cr(VI) and nitrate removal

A green synthesized zero valent iron (ZVI) and a physically activated carbon derived from banana peel waste (BPAC) were co-precipitated to fabricate a composite adsorbent (ZVI-BPAC). Fe-SEM and TEM studies reveal the better dispersion of the nano-particles of the composite, lesser particle aggregation and smaller nano-sized dimension as compared to that for the ZVI. Biogenic nature of the composite is indicated by its surface chemical composition (C: 55%; Fe: 24%; O: 19%) as evident from EDAX studies. FTIR studies confirm the successful fabrication of ZVI particles onto the surface of the BPAC. The composite demonstrated good potential for the removal of both Cr(VI) (74%) and NO3– (48.5%) from aqueous medium. The adsorptive removal process was pH dependent with maximum removal occurring at pH 3 at an optimum contact time of 30 mins using a dosage of 0.7 g/L and from an initial adsorbate concentration of 20 mg/L. The study reveals the application of a novel green fabrication process for the development of a biogenic nanocomposite. ZVI-BPAC demonstrated good potential for the significant removal of Cr(VI) and NO3– from aqueous solution.

Obtaining and study of physical-chemical properties of porous materials based on kaolin

The object of research is kaolin from the Hlukhovetsky deposit (Ukraine). On its basis, granulated sorbent materials were obtained with the addition of various amounts of cellulose as a pore former. After forming the samples, they were dried and fired at a temperature of 800 °C. The obtained granules with a size of 8–9 mm were modified with zero-valent iron. The physicochemical, including sorption properties of granular composites were studied. Using scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), the morphology of the obtained samples was investigated and the presence of zero-valent iron particles on the surface and in the pores of the sorbents was confirmed. Based on desorption experiments, it was determined by chemical analysis that the Fe0 content in modified samples with increased pore former content increases from 0.01 g/g of granules for a sample containing 1% cellulose to 0.016 g/g for a carrier with 3 % pore former. The specific surface area and pore volume of the samples were determined by the method of low-temperature adsorption-desorption of nitrogen. Thus, with an increase in the content of the pore former in the ceramic mass, the specific surface of both unmodified and modified samples slightly decreases. Thus, with a cellulose content of 1 %, it is 20 m2/g and 17 m2/g, respectively. When the pore former is increased to 3%, these values are 15 m2/g and 12 m2/g. After applying a layer of zero-valent iron on porous granules, the volume of pores decreases, which is due to the formation of agglomerates of iron particles during synthesis. The study of the sorption capacity of the obtained sorbents with respect to Cr(VI) from model solutions containing a mixture of metal cations (copper, cadmium, cobalt, zinc) showed that granular materials exhibit sorption capacity for metal anions, even in the presence of cations. The amount of chromium sorption naturally increases for modified samples with an increase in the cellulose content in them. However, for model solutions that do not additionally contain metal cations, the sorption value is somewhat higher. Thus, for a sample with a 3 % pore former content, the sorption value is 0.7 mg/g and 0.9 mg/g, respectively, at an initial chromium(VI) concentration of 10 mg/g. The obtained experimental data indicate that the obtained porous granular sorbents based on kaolin can be used in the further treatment of wastewater from electroplating enterprises, which contain a mixture of pollutants in both anionic and cationic forms.

Degradation of Chloroform by Zerovalent Iron: Effects of Mechanochemical Sulfidation and Nitridation on the Kinetics and Mechanism.

Chloroform (CF) is a widely used chemical reagent and disinfectant and a probable human carcinogen. The extensive literature on halocarbon reduction with zerovalent iron (ZVI) shows that transformation of CF is slow, even with nano, bimetallic, sulfidated, and other modified forms of ZVI. In this study, an alternative method of ZVI modification─involving simultaneous sulfidation and nitridation through mechanochemical ball milling─was developed and shown to give improved degradation of CF (i.e., higher degradation rate and inhibited H2 evolution reaction). The composite material (denoted as S-N(C)-ZVI) gave synergistic effects of nitridation and sulfidation on CF degradation. A complete chemical reaction network (CRN) analysis of CF degradation suggests that O-nucleophile-mediated transformation pathways may be the main route for the formation of the terminal nonchlorinated products (formate, CO, and glycolic polymers) that have been used to explain the undetected products needed for mass balance. Material characterizations of the ZVI recovered after batch experiments showed that sulfidation and nitridation promoted the formation of Fe3O4 on the S-N(C)-ZVI particles, and the effect of aging on CF degradation rates was minor for S-N(C)-ZVI. The synergistic benefits of sulfidation and nitridation on CF degradation were also observed in experiments performed with groundwater.