Modeling the Permeability Loss of Metallic Iron Water Filtration Systems

Over the past 30 years the literature has burgeoned with in situ approaches for groundwater remediation. Of the methods currently available, the use of metallic iron (Fe⁰) in permeable reactive barrier (PRB) systems is one of the most commonly applied. Despite such interest, an increasing amount of experimental and field observations have reported inconsistent Fe⁰ barrier operation compared to contemporary theory. In the current work, a critical review of the physical chemistry of aqueous Fe⁰ corrosion in porous media is presented. Subsequent implications for the design of Fe⁰ filtration systems are modeled. The results suggest that: (i) for the pH range of natural waters (>4.5), the high volumetric expansion of Fe⁰ during oxidation and precipitation dictates that Fe⁰ should be mixed with a non‐expansive material; (ii) naturally occurring solute precipitates have a negligible impact on permeability loss compared to Fe⁰ expansive corrosion; and (iii) the proliferation of H₂ metabolizing bacteria may contribute to alleviate permeability loss. As a consequence, it is suggested that more emphasis must be placed on future work with regard to considering the Fe⁰ PRB system as a physical (size‐exclusion) water filter device.     

Enhancing the Sustainability of Household Fe0/Sand Filters by Using Bimetallics and MnO2

Filtration systems containing metallic iron as reactive medium (Fe⁰ beds) have been intensively used for water treatment during the last two decades. The sustainability of Fe⁰ beds is severely confined by two major factors: (i) reactivity loss as result of the formation of an oxide scale on Fe⁰ and (ii) permeability loss due to pore filling by generated iron corrosion products. Both factors are inherent to iron corrosion at pH > 4.5 and are common during the lifespan of a Fe⁰ bed. It is of great practical significance to improve the performance of Fe⁰ beds by properly addressing these key factors. Recent studies have shown that both reactivity loss and permeability loss could be addressed by mixing Fe⁰ and inert materials. For a non‐porous additive like quartz, the threshold value for the Fe⁰ volumetric proportion is 51%. Using the Fe⁰/quartz system as reference, this study theoretically discusses the possibility of (i) replacing Fe⁰ by bimetallic systems (e.g., Fe⁰/Cu⁰), or (ii) partially replacing quartz by a reactive metal oxide (MnO₂ or TiO₂) to improve the efficiency of Fe⁰ beds. Results confirmed the suitability of both tools for sustaining Fe⁰ bed performance. It is shown that using a Fe⁰:MnO₂ system with the volumetric proportion 51:49 will yield a filter with 40% residual porosity at Fe⁰ depletion (MnO₂ porosity 62%). This study improves Fe⁰ bed design and can be considered as a basis for further refinement and detailed research for efficient Fe⁰ filters.     

Designing Iron‐Amended Biosand Filters for Decentralized Safe Drinking Water Provision

There are ongoing efforts to render conventional biosand filters (BSF) more efficient for safe drinking water provision. One promising option is to amend BSF with a reactive layer containing metallic iron (Fe⁰). The present communication presents some conceptual options for efficient Fe⁰‐amended BSF in its fourth generation. It is shown that a second fine‐sand layer should be placed downwards from the Fe⁰‐reactive layer to capture dissolved iron. This second fine‐sand layer could advantageously contain adsorbing materials (e.g. activated carbons, wooden charcoals). An approach for sizing the Fe⁰‐reactive layer is suggested based on 3 kg Fe⁰ per filter. Working with the same Fe⁰ load will ease comparison of results with different materials and the scaling up of household BSF to large scale community slow sand filters (SSF).     

Extending Service Life of Household Water Filters by Mixing Metallic Iron with Sand

The use of metallic iron filters (Fe⁰ filters) has been discussed as a promising low‐cost option for safe drinking water production at household level. Filter clogging due to the volumetric expansive nature of iron corrosion has been identified as the major problem of Fe⁰ filters. Mixing Fe⁰ and sand (yielding Fe⁰/sand filters) has been proposed as a tool to extent filter service life. However, no systematic discussion rationalizing Fe⁰/sand mixtures is yet available. This communication theoretically discussed suitable Fe⁰/sand proportions for efficient filters. Results suggested that Fe⁰/sand filters should not contain more that 50 vol% Fe⁰ (25 wt% when Fe⁰ is mixed with quartz). The actual Fe⁰ percentage in a filter will depend on its intrinsic reactivity.     

Degradation of Phenol in Aqueous Solution by Fenton,Sono‐Fenton and Sono‐photo‐Fenton Methods

The present work focuses on the performance of Fenton, sono‐Fenton, and sono‐photo‐Fenton processes for the oxidation of phenol present in aqueous solution. The effects of H₂O₂ concentration, Fe²⁺ concentration, pH, and initial phenol concentration on the oxidation of phenol were studied. The optimum Fe²⁺ and H₂O₂ concentrations for the Fenton process were 45 and 800 mg/L, respectively. For the sono‐Fenton process, the optimum Fe²⁺ and H₂O₂ concentrations were 30 and 800 mg/L, respectively. The optimal conditions for the sono‐photo‐Fenton process were found to be 20 mg/L of Fe²⁺ and 700 mg/L of H₂O₂. The optimum pH was found to be 3 for the processes investigated in the present study. The analysis of results showed that the sono‐photo‐Fenton method reduced the Fe²⁺ concentration by 30–50% and the H₂O₂ concentration by 12.5%. It was found that the sono‐photo‐Fenton technique showed better performance than the Fenton and sono‐Fenton processes for the oxidation of phenol. A lumped kinetic model was used to predict the chemical oxygen demand reduction and the model was found to fit the data.     

Relevant Reducing Agents in Remediation Fe0/H2O Systems

Metallic iron (Fe⁰) is often reported as a reducing agent for environmental remediation. There is still controversy as to whether Fe⁰ plays any significant direct role in the process of contaminant reductive transformation. The view that Fe⁰ is mostly a generator of reducing agents (e.g. H, H₂ and Fe^II) and Fe oxyhydroxides has been either severely refuted or just tolerated. The tolerance is based on the simplification that, without Fe⁰, no secondary reducing agents could be available. Accordingly, Fe⁰ serves as the original source of electron donors (including H, H₂ and Fe^II). The objective of this communication is to refute the named simplification and establish that quantitative reduction results from secondary reducing agents. For this purpose, reports on aqueous contaminant removal by Al⁰, Fe⁰ and Zn⁰ are comparatively discussed. Results indicated that reduction may be quantitative in aqueous systems containing Fe⁰ and Zn⁰ while no significant reduction is observed in Al⁰/H₂O systems. Given that Al⁰ is a stronger reducing agent than Fe⁰ and Zn⁰, it is concluded that contaminant reduction in Fe⁰/H₂O systems results from synergic interactions between H/H₂ and Fe^II within porous Fe oxyhydroxides. This conclusion corroborates the operating mode of Fe⁰ bimetallics as H/H₂ producing systems for indirect contaminant reduction.     

S‐Doped Magnetic Mesoporous Carbon for Efficient Adsorption of Methyl Orange from Aqueous Solution

A simple and rapid soft‐templating coupled with one‐pot solvent thermal method is developed to synthesize S‐doped magnetic mesoporous carbon (S‐doped MMC). In this method, phenolic resin is used as a carbon precursor and Pluronic copolymer P123 is used as a template and 2,5‐dimercapto‐1,3,4‐thiadiazole is used as sulfur source. Prepared S‐doped MMC processes a high specific surface area, the Fe₃O₄ particles are well embedded in the mesoporous carbon walls that exhibit a strong magnetic response, and the hydrated iron nitrate loading amount of 0.808 g is the best. Batch adsorption experiments are carried out at different pH, initial concentration, temperature, and contact time on the adsorption of methyl orange (MO) by S‐doped MMC. The kinetic data of the adsorption process are better fitted with pseudo‐second‐order model than the pseudo‐first‐order model. Langmuir model is more suitable for the equilibrium data than Freundlich model. The thermodynamic parameters including ΔG⁰, ΔH⁰, and ΔS⁰ indicate that the adsorption is a feasible, spontaneous, and endothermic process. Finally, it is found that the coexistence of PO₄^3?, NO₃^?, SO₄^2?, Cl^?, and CO₃^2? does not influence the adsorption process. These results illustrate S‐doped MMC can be an efficient adsorbent for the removal of MO from wastewater.     

Chrome spinel in normal MORB‐type greenstones from the Paleozoic–Mesozoic Mino terrane,East Takayama area,central Japan: Crystallization course with a U‐turn

Phenocrystic chrome spinel crystallized in normal MORB‐type greenstones in the East Takayama area. Associated phenocryst minerals show a crystallization sequence that was olivine first, followed by plagioclase, and finally clinopyroxene. Chrome spinel ranges from 0.54 to 0.77 in Mg/(Mg+Fe²⁺) and 0.21 to 0.53 in Cr/(Cr+Al); the Fe³⁺ content varies from 0.07 to 0.22 p.f.u. (O = 4). Significant compositional differences of spinel were observed among the phenocryst mineral assemblages. Chrome spinel in the olivine–spinel assemblage shows a wide range in Cr/(Cr+Al), and is depleted in Fe²⁺ and Fe³⁺. Chrome spinel in the olivine–plagioclase–clinopyroxene–spinel assemblage is Fe²⁺‐ and Fe³⁺‐rich at relatively high Cr/(Cr+Al) ratios. Basalt with the olivine–plagioclase–spinel assemblage contains both aluminous spinel and Fe²⁺‐ and Fe³⁺‐rich spinel. The assumed olivine–spinel equilibrium suggests that chrome spinel in the olivine–spinel assemblage changed in composition from Cr‐ and Fe²⁺‐rich to Al‐ and Mg‐rich with the progress of fractional crystallization. Chrome spinel in the olivine–plagioclase–clinopyroxene–spinel assemblage, on the other hand, exhibits the reversed variations in Mg/(Mg+Fe²⁺) and in Cr/(Cr+Al) ratios that decrease and increase with the fractional crystallization, respectively. The entire crystallization course of chrome spinel, projected onto the Mg/(Mg+Fe²⁺)–Cr/(Cr+Al) diagram, exhibits a U‐turn, and appears to be set on a double‐lane route. The U‐turn point lies in the compositional field of chrome spinel in the olivine–plagioclase–spinel assemblage, and may be explained by plagioclase fractionation that began during the formation of the olivine–plagioclase–spinel assemblage.     

Effect of Pumice and Sand on the Sustainability of Granular Iron Beds for the Aqueous Removal of CuII,NiII, and ZnII

Current knowledge of the basic principles underlying the design of Fe⁰ beds is weak. The volumetric expansive nature of iron corrosion was identified as the major factor determining the sustainability of Fe⁰ beds. This work attempts to systematically verify developed concepts. Pumice and sand were admixed to 200 g of Fe⁰ in column studies (50:50 volumetric proportion). Reference systems containing 100% of each material have been also investigated. The mean grain size of the used materials (in mm) were 0.28 (sand), 0.30 (pumice), and 0.50 (Fe⁰). The five studied systems were characterized (i) by the time dependent evolution of their hydraulic conductivity (permeability) and (ii) for their efficiency for aqueous removal of Cu^II, Ni^II, and Zn^II (about 0.3 mM of each). Results showed unequivocally that (i) quantitative contaminant removal was coupled to the presence of Fe⁰, (ii) additive admixture lengthened the service life of Fe⁰ beds, and (iii) pumice was the best admixing agent for sustaining permeability while the Fe⁰/sand column was the most efficient for contaminant removal. The evolution of the permeability was well‐fitted by the approach that the inflowing solution contained dissolved O₂. The achieved results are regarded as starting point for a systematic research to optimize/support Fe⁰ filter design.     

Effect of SO on 1,1,1‐Trichloroethane Degradation by Fe0 in Aqueous Solution

Sulfate in groundwater has been previously shown to change the reactivity of Fe⁰ in permeable reactive barriers for reducing chlorinated organics. To better understand the effect and mechanism of SO, the degradation of 1,1,1‐trichloroethane (TCA) by Fe⁰ in unbuffered aqueous solutions with and without SO was investigated. In a Fe⁰‐TCA‐H₂O system with initial pH of 2.0 to 10.0, the maximum removal rate of TCA was achieved at the initial pH 6.0 with pseudo‐first‐order constant K_obs 9.0 × 10^?3/min. But in a Fe⁰‐TCA‐Na₂SO₄‐H₂O system, the removal rate of TCA decreased remarkably with a reduction in K_obs to 1.0 × 10^?3/min, and the pH varied from 6.0 to 9.6, indicating an inhibition of TCA dehydrochlorination by SO. Sulfate remarkably inhibited TCA degradation via changing the route of Fe⁰ dissolution. It accelerated the dissolution of Fe⁰ and transformed the intermediate form Fe(OH)_ads to Fe₂(SO₄)_ads, which weakened the affinity between Fe and TCA, and thus depressed the degradation of TCA by Fe⁰.     

Adsorption of Two Taste and Odor Compounds IPMP and IBMP by Granular Activated Carbon in Water

Granular activated carbon (GAC) adsorption of two representative taste and odor (T & O) compounds, 2‐isopropyl‐3‐methoxy pyrazine (IPMP), and 2‐isobutyl‐3‐methoxy pyrazine (IBMP), in drinking water was investigated. Results show that the modified Freundlich equation best fit the experimental data during the adsorption isotherm tests, and the pseudo first‐order kinetics and intra‐particle diffusion kinetics well described the adsorption kinetics pattern. The calculated thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) indicated a spontaneous and endothermic adsorption process. Factors affecting the treatment efficiency were carefully evaluated. Acidic and alkaline conditions both favored GAC adsorption of IPMP and IBMP, especially the former. With the GAC dosage increasing, the first order adsorption rates increased, while the intra‐particle adsorption rates decreased. Within 12 h, 200 mg/L GAC could remove >90% of 150 µg/L IPMP and IBMP via adsorption at pH 3–11. Therefore, GAC is a promising treatment technology to control the T & O compounds associated water pollution.     

Efficacy of Hollow‐Fiber Ultrafiltration for Microbial Sampling in Groundwater

The goal of this study was to test hollow‐fiber ultrafiltration as a method for concentrating in situ bacteria and viruses in groundwater samples. Water samples from nine wells tapping a shallow sandy aquifer in a densely populated village in Bangladesh were reduced in volume approximately 400‐fold using ultrafiltration. Culture‐based assays for total coliforms and Escherichia coli, as well as molecular‐based assays for E. coli, Bacteroides, and adenovirus, were used as microbial markers before and after ultrafiltration to evaluate performance. Ultrafiltration increased the concentration of the microbial markers in 99% of cases. However, concentration factors (CF = post‐filtration concentration/pre‐filtration concentration) for each marker calculated from geometric means ranged from 52 to 1018 compared to the expected value of 400. The efficiency was difficult to quantify because concentrations of some of the markers, especially E. coli and total coliforms, in the well water (WW) collected before ultrafiltration varied by several orders of magnitude during the period of sampling. The potential influence of colloidal iron oxide precipitates in the groundwater was tested by adding EDTA to the pre‐filtration water in half of the samples to prevent the formation of precipitates. The use of EDTA had no significant effect on the measurement of culturable or molecular markers across the 0.5 to 10 mg/L range of dissolved Fe²⁺ concentrations observed in the groundwater, indicating that colloidal iron did not hinder or enhance recovery or detection of the microbial markers. Ultrafiltration appears to be effective for concentrating microorganisms in environmental water samples, but additional research is needed to quantify losses during filtration.     

Separation and Preconcentration of Boron with a Glucamine Modified Novel Magnetic Sorbent

A novel, simple method based on magnetic separation was developed for analytical purposes. In this method, N‐methyl‐D‐glucamine (NMDG) modified magnetic microparticles that were synthesized by using the sol‐gel method were used for the selective extraction and preconcentration of boron from aqueous solutions. This method combines the simplicity and selectivity of solvent extraction with the easy separation of magnetic microparticles from a solution with a magnet without any preliminary filtration step. The structure of the prepared γ‐Fe₂O₃‐SiO₂‐NMDG (magnetic sorbent) composites were characterized by using X‐ray diffraction (XRD), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). The influence of different parameters on the sorbent capacity, such as the sorption/desorption of boron, magnetic sorbent dosage, pH, equilibrium time, type, and amount of stripping solution, were evaluated by using the magnetic sorbent. Any equilibrium pH greater than 6 can be used for sorption. Desorption from the sorbent was carried out by using 1.0 M HCl. The sorption and desorption efficiency of the γ‐Fe₂O₃‐SiO₂‐NMDG was found as 92.5 ± 0.5% and 99.8 ± 6%, respectively.     

Detrital chromian spinels from beach placers of Andaman Islands,India: A perspective view of petrological characteristics and variations of the Andaman ophiolite

Along the east coast of the Andaman Islands, abundant detrital chromian spinels frequently occur in black sands at the confluence of streams meeting the Andaman Sea. The mineral chemistry of these detrital chromian spinels has been used in reconstructing the evolutionary history of the Andaman ophiolite. The chromian spinels show wide variation in compositional parameters such as Cr# [= Cr/(Cr + A1) atomic ratio] (0.13–0.91), Mg# [= Mg/(Mg + Fe²⁺) atomic ratio] (0.23–0.76), and TiO₂ (<0.05–3.9 wt%). The YFe³⁺[= 100Fe³⁺/(Cr + A1 + Fe³⁺) atomic ratio] is remarkably low (usually <10 except for south Andaman). The ranges of chemical composition of chromian spinels are different in each locality. The spinel compositions show very depleted signatures over the entire island, which suggests that all massifs in the Andaman ophiolite were affected under island‐arc conditions. Although the degree of depletion varies in different parts of the island, a directional change in composition of the detrital chromian spinels from south to north is evident. Towards the north the detrital chromian spinels point to less‐depleted source rocks in contrast to relatively more depleted towards the south. The possibilities to explain this directional change are critically discussed in the context of the evolution of Andaman ophiolite.     

Distinguishing Iron-Reducing from Sulfate-Reducing Conditions

Ground water systems dominated by iron‐ or sulfate‐reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe²⁺) and sulfide (sum of H₂S, HS^?, and S⁼ species and denoted here as “H₂S”). This approach is based on the observation that concentrations of Fe²⁺ and H₂S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe²⁺ concentrations are high, H₂S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe²⁺ with H₂S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron‐ and the sulfate‐reducing microorganisms that catalyze the production of Fe²⁺ and H₂S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe²⁺ and H₂S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H₂) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe²⁺/H₂S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H₂～0.2 to 0.8 nM). Conversely, if the Fe²⁺/H₂S ratio was less than 0.30, consistent sulfate‐reducing (H₂～1 to 5 nM) conditions were observed over time. Concomitantly high Fe²⁺ and H₂S concentrations were associated with H₂ concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron‐ and sulfate‐reducing zones or concomitant iron and sulfate reduction under nonelectron donor–limited conditions. These observations suggest that Fe²⁺/H₂S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.     

Color Removal from Synthetic Textile Wastewater by Sono‐Fenton Process

In this study, the oxidative decolorization of C.I. reactive yellow 145 (RY 145) from synthetic textile wastewater including RY 145 and polyvinyl alcohol by Fenton and sono‐Fenton processes which are the combination of Fenton process with ultrasound has been carried out. The effects of some operating parameters which are the initial pH of the solution, the initial concentration of Fe²⁺, H₂O₂, and the dye, temperature, and agitation speed on the color and chemical oxygen demand (COD) removals have been investigated. The optimum conditions have been found as [Fe²⁺] = 20 mg/L, [H₂O₂] = 20 mg/L, pH 3 for Fenton process and [Fe²⁺] = 20 mg/L, [H₂O₂] = 15 mg/L, pH 3 for sono‐Fenton process by indirectly sonication at 35 kHz ultrasonic frequency and 80 W ultrasonic power. The color and COD removal efficiencies have been obtained as 91 and 47% by Fenton process, and 95 and 51% by sono‐Fenton processes, respectively. Kinetic studies have been performed for the decolorization of RY 145 under optimum conditions at room temperature. It has been determined that the decolorization has occurred rapidly by sono‐Fenton process, compared to Fenton process.     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

Optimization of a Photo‐assisted Fenton Oxidation Process: A Statistical Model for MDF Effluent Treatment

In the present study, the effects of initial COD (chemical oxygen demand), initial pH, Fe²⁺/H₂O₂ molar ratio and UV contact time on COD removal from medium density fiberboard (MDF) wastewater using photo‐assisted Fenton oxidation treatment were investigated. In order to optimize the removal efficiency, batch operations were carried out. The influence of the aforementioned parameters on COD removal efficiency was studied using response surface methodology (RSM). The optimal conditions for maximum COD removal efficiency from MDF wastewater under experimental conditions were obtained at initial COD of 4000 mg/L, Fe²⁺/H₂O₂ molar ratio of 0.11, initial solution pH of 6.5 and UV contact time of 70 min. The obtained results for maximum COD removal efficiency of 96% revealed that photo‐assisted Fenton oxidation is very effective for treating MDF wastewater.     

Pickling Waste as an Inexpensive Iron Source for Fenton Oxidation of Synthetic Dye Bath Waste

A simple, low cost, highly effective, and useful Fenton oxidation treatment of synthetic dye bath waste with pickling liquor as a source of iron (Fe²⁺ catalyst) is reported. Optimizations of contact time, Fe²⁺ and H₂O₂ doses are carried out. Oxidative de‐colorization and degradation of Reactive Blue 4 and Reactive Orange 16 was measured in terms of decrease in absorbance at their wavelength of maximum absorption (RB4, 599 nm; and RO16, 493 nm) and also as reduction in chemical oxygen demand (COD). Approximately, 62% COD was removed in 2 h at optimized doses of Fe²⁺ (8.95 mM) and H₂O₂ (61.8 mM) by using pickling waste as a source of Fe²⁺ catalyst. Similar performance efficiency was observed when neat FeSO₄ was used as a source of Fe²⁺, indicating that pickling liquor can be a low cost source of Fe²⁺ to treat synthetic dye bath waste by Fenton method.     

Synthesis of Calix[4]arene‐grafted Magnetite Nanoparticles and Evaluation of Their Arsenate as Well as Dichromate Removal Efficiency

In this study, 5,17‐bis‐[(4‐benzylpiperidine)methyl]‐25,26,27,28‐tetrahydroxy‐calix[4]arene ( 3 ) has been prepared by the treatment of calix[4]arene with a secondary amine (4‐benzylpiperidine) and formaldehyde by means of Mannich reaction. The prepared Mannich base ( 3 ) has been grafted onto [3‐(2,3‐epoxypropoxy)‐propyl]‐trimethoxysilane‐modified Fe₃O₄ magnetite nanoparticles (EPPTMS‐MN) in order to obtain 5,17‐bis‐[(4‐benzylpiperidine)methyl]‐25,26,27,28‐tetrahydroxy calix[4]arene‐grafted EPPTMS‐MN (BP‐calix[4]arene‐grafted Fe₃O₄). All new compounds were characterized by a combination of FTIR and ¹H‐NMR analyses. The morphology of the magnetic nanoparticles was examined by transmission electron microscopy. Moreover, the studies regarding the removal of arsenate and dichromate ions from the aqueous solutions were also carried out by using 5,17‐bis‐[(4‐benzylpiperidine)methyl]‐25,26,27,28‐tetrahydroxy‐calix[4]arene in liquid–liquid extraction and BP‐calix[4]arene‐grafted Fe₃O₄ ( 4 ) in solid–liquid extraction experiments. The extraction results indicated that 3 is protonated at proton‐switchable binding sites in acidic conditions. Hence, facilitating binding of arsenate and dichromate is resulted from both electrostatic interactions and hydrogen bonding. To understand the selectivity of 3 , the retention of dichromate anions in the presence of Cl⁻, NO, and SO anions at pH 1.5 was also examined.