Preparation,characterization, and kinetics of nanoscale iron in nitrate nitrogen removal from polluted water

The aim of this study was to examine the production of nanoscale ions via the liquid phase reduction method and the effectiveness of the removal of nitrate nitrogen (NO₃^?–N) as well as measure the products and kinetics of the reactions. The nanoparticles obtained were approximately 50 nm in diameter and the main component was iron (Fe). This custom-made nanoscale Fe was highly positively charged, and reacted rapidly with NO₃^?–N in oxygen-free and neutral conditions at room temperature. A 90% removal rate was achieved when the reaction occurred for 30 min in simulation sample water with vigorous shaking at 250 r/min at NO₃^?–N concentrations of 30, 50, 80 or120 mg N/L. The nanometer Fe dosage was maintained throughout the experiment at 4 g/L. A first-order kinetics equation was applied to the obtained experimental data which followed a pseudo first-order reaction. Data demonstrated that the removal of nitrate nitrogen from polluted groundwater using a nanoscale Fe iron was effective and rapid.     

Iron-doped copper 1,4-benzenedicarboxylate as photo-Fenton catalyst for degradation of methylene blue

Abstract

A metal-organic framework of iron-doped copper 1,4-benzenedicarboxylate was synthesized and, for the first time, utilized as a heterogeneous photo-Fenton catalyst for degradation of methylene blue dye in aqueous solution under visible light irradiation. The synthesized materials were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and energy-dispersive X-ray spectroscopy. The influence factors, kinetics, and stability of the synthesized catalysts were investigated in detail. Iron-doped copper 1,4-benzenedicarboxylate showed higher degradation efficiency than pure copper 1,4-benzenedicarboxylate. An almost complete degradation was achieved within 70?min under visible light irradiation at a solution pH of 6, a catalyst loading of 1?g?L^?1, a H₂O₂ dosage of 0.05?mol L^?1 and methylene blue concentration of 50?mg?L^?1. Recycling studies demonstrated that the iron-doped copper 1,4-benzenedicarboxylate is a promising heterogeneous photo-Fenton catalyst for long-term removal of methylene blue dye from industrial wastewater.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min^?1 when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min^?1 were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

Synthesis of nanoiron by microemulsion with Span/Tween as mixed surfactants for reduction of nitrate in water

Denitrification of nitrate in groundwater using iron nanoparticles has received increasing interest in recent years. In order to fabricate iron nanoparticles with homogeneously spherical shape and narrow size distribution, a simple and “green” method was developed to synthesize iron nanoparticles. The conventional microemulsion methods were modified by applying Span 80 and Tween 60 as mixed surfactants. The maximum content of water in the Water-in-oil (W/O) microemulsion and its appropriate forming conditions were found, and then the microemulsion system consisting of saturated Fe²⁺ solution was used to synthesize α-Fe ultrafine particles by redox reaction. The nanoparticles were characterized by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the average diameter of the particle is about 80–90 nm. The chemical activity of the obtained iron nanoparticles was studied by the denitrification experiment of nitrate. The results show that under the experimental conditions, iron removed most of the 80 mg/L nitrate within 30 min. The mass balance of nitrate reduction with nanoscale Fe indicates that endproducts are mainly ammonia. Two possible reaction pathways for nitrate reduction by nanoscale iron particles have been proposed in this work.     

Adsorption of phosphate ions from water using a novel cellulose-based adsorbent

A novel cellulose-based adsorbent, iron(III)-coordinated amino-functionalised poly(glycidylmethacrylate)-grafted cellulose [Fe(III)–AM-PGMACell] was developed for the removal of phosphate from water and wastewater. The scanning electron micrograph showed that AM-PGMACell has a rougher surface than cellulose and the adsorption of Fe(III) on AM-PGMACell made the surface even rougher. Infrared spectroscopy revealed that amino groups on the surface of AM-PGMACell complexed with Fe(III) played an important role in the removal of phosphate from solutions. X-Ray diffraction patterns showed a decrease in crystallinity after graft copolymerisation onto cellulose. The effects of contact time, initial sorbate concentration, pH, agitation speed, dose of adsorbent and temperature on the removal process were investigated. Maximum removal of 99.1% was observed for an initial concentration of 25 mg·L ^?1 at pH 6.0 and an adsorbent dose of 2.0 g·L ^?1. A two-step pseudo-first-order kinetic model and Sips isotherm model represented the measured data very well. Complete removal of 11.6 mg·L ^?1 phosphate from fertiliser industry wastewater was achieved by 1.6 g·L ^?1 Fe(III)–AM-PGMACell. The adsorbent exhibited very high reusability for several cycles. Overall, the study demonstrated that Fe(III)–AM-PGMACell can be used as an efficient adsorbent for the removal and recovery of phosphate from water and wastewater.     

Photodegradation of an azo dye by silver-doped nano-particulate titanium dioxide

The synthesis of silver doped nano-particulate titanium dioxide (Ag/TiO₂) using a microemulsion method and an investigation of its photocatalytic activity for the degradation of Acid Red 27 in distilled water under UV-irradiation is reported. The prepared Ag/TiO₂ is characterized using transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The size of the Ag nanoparticles is around 5–15?nm, with almost uniform distribution on the TiO₂ particles. The efficiency of the photocatalytic process is evaluated to establish the optimum conditions, found to be at 2?wt% of Ag loading on TiO₂, catalyst dosage of 400?mg?L^?1, and calcination temperature of 300°C. Complete decolorization of the dye solution on Ag/TiO₂ was observed in 20?min of UV irradiation in the optimum conditions.     

Biosynthesis of iron nanoparticles and their application in removing phosphorus from aqueous solutions

This paper reports the biosynthesis of nanoscale zero-valent iron (nZVI) using the extracts of Shirazi thyme leaf (Th-nZVI) and pistachio green hulls (P-nZVI). Scanning electron microscopy verified the successful synthesis of the poorly crystalline nZVI with a spherical shape and diameter in the range of 40–70 nm. According to X-ray diffraction and Fourier transform infrared spectroscope analyses, the synthesised nZVI were composed of iron oxides nanoparticles and ployphenol obtained from Shirazi thyme leaf and pistachio green hulls extracts acting as both reducing and capping agents. The phosphorus removal efficiency of Th-nZVI and P-nZVI increased with time and reached equilibrium at about 4 and 2h, respectively. Sorption of phosphorus on both sorbents was observed to be pH-dependent with maximum phosphorus removal occurring in the pH range of 2–5. Langmuir, Freundlich, Redlich–Peterson, and Temkin models were used to describe phosphorus sorption at pH 5 and maximum sorption capacity for Th-nZVI and P-nZVI was about 40.52 and 29.33?mg?g^?1, respectively. Correlation coefficient (R²) and standard errors of estimate showed that the Elovich model was better than other models at describing the kinetic data. These results suggested that the synthesised nZVI with Shirazi thyme leaf and pistachio green hulls extracts could be employed as an efficient sorbent for the remediation of phosphorus from contaminated water sources.     

Toxicity of metals to tadpoles of the common Sunda toad,Duttaphrynus melanostictus

Tadpoles of the common freshwater Sunda toad, Duttaphrynus melanostictus (Amphibia, Bufonidae), were exposed for a 4-day period under laboratory conditions to copper (Cu), cadmium (Cd), zinc (Zn), lead (Pb), nickel (Ni), iron (Fe), aluminum (Al), and manganese (Mn) at various concentrations. Mortality was assessed and median times of death (LT₅₀) and lethal concentrations (LC₅₀) were calculated. LT₅₀ and LC₅₀ increased with the decrease in mean exposure times and concentrations for all metals. LC₅₀ (96?h) for Cu, Cd, Zn, Pb, Ni, Fe, Al, and Mn were 0.03, 0.3, 4.2, 1.5, 8.8, 0.4, 1.9, and 39?mg?L^?1, respectively. Cu was the most toxic to D. melanostictus, followed by Cd, Fe, Al, Pb, Zn, Ni, and Mn (Cu?>?Cd?>?Fe?>?Al?>?Pb?>?Zn?>?Ni?>?Mn). Duttaphrynus melanostictus is similarly sensitive to these metals as other amphibian tadpoles.     

Effects of nanoparticles on Daphnia magna population dynamics

Spherical TiO₂ nanoparticles (npTiO₂) were prepared by controlled hydrolysis of tetraethoxy orthotitanate under a nitrogen atmosphere. ZnO nanoparticles (npZnO) were prepared using hydrothermal methods. The crystal structure, chemical, thermal and morphological properties of npZnO and npTiO₂ were characterised using Fourier Transform Infrared Spectrometer, enery-dispersive X-ray spectroscopy, X-ray diffraction, and scanning electron microscope techniques. The short- and long-term experiments were started with neonates taken from the same culture and laboratory condition. In the acute experiments, npTiO₂, npZnO, and cocktail concentrations were applied. 96h-LC₅₀ values were 1.8, 0.7, and 0.1?mg?L^?1, respectively (p?<?.05). For the chronic experiments, different npTiO₂ concentrations were performed. 21d-LC₅₀ value was 1.0?mgL^?1 (p?<?.05). Morphometry became progressively worse in concentrations of more than 1?mgL^?1 npTiO₂. Neonate and young individuals were more sensitive to death because of their low tolerance. This result was affected by population progeny and growth rates (p?<?.05). While control and 0.5?mgL^?1 npTiO₂ groups were determined as growing population, 1.5 and 2?mgL^?1 npTiO₂ groups had decreased population size as R₀ values. Consequently, the relationships between nanoparticle accumulation within Daphnia magna and its population structure and body morphometry for each concentration were important indicators. Its tolerance level to nanoparticles under laboratory conditions reflected its replacement and behaviour in the ecosystem.     

Chemically modified biochar produced from conocarpus waste increases NO<Subscript>3</Subscript> removal from aqueous solutions

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO₃ removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO₃ sorption capacity of 45.36 mmol kg^?1 predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO₃ sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m² g^?1) and formation of strong ionic complexes with NO₃. At an initial pH of 2, more than 89 % NO₃ removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.     

Removal of arsenic by Acidothiobacillus ferrooxidans bacteria in bench scale fixed-bed bioreactor system

In the present study arsenic contaminated simulated water and groundwater was treated by the combination of biological oxidation of tri-valent arsenite [As (III)] to penta-valent arsenate [As (V)] in presence of Acidothiobacillus ferrooxidans bacteria and its removal by adsorptive filtration in a bioreactor system. This method includes the immobilisation of A.ferrooxidans on Granulated Activated Carbon (GAC) capable of oxidising ferrous [Fe (II)] to ferric [Fe (III)]. The Fe (III) significantly converts the As (III) to As (V) and ultimately removed greater than 95% by the bed of GAC, limestone, and sand. The significant influence of Fe (II) concentration (0.1–1.5?gL^?1), flowrate (0.06–0.18?Lh^?1), and initial As (III) concentration (100–1000?µgL^?1) on the arsenic removal efficiency was investigated. The simulated water sample containing the different concentration of As (III) and other ions was used in the study. The removal of other co-existing ions present in contaminated water was also investigated in column study. The concentration of arsenic was found to be <10?µgL^?1 which is below Maximum Contaminant Level (MCL) as per WHO in treated water. The results confirmed that the present system including adsorptive-filtration was successfully used for the treatment of contaminated water containing As (III) ions.     

One-step synthesis of bentonite-supported nanoscale Fe/Ni bimetals for rapid degradation of methyl orange in water

Although nanoscale zero-valent iron (nano-Fe⁰) is used to remediate pollutants, this reagent still presents stability and reactivity issues. To solve those issues, we synthesized bentonite-supported nanoscale iron bimetals B-Fe/Ni and B-Fe/Pd. We then used those reagents to degrade the methyl orange dye in water. Results of scanning electron microscopy and X-ray diffraction showed that the presence of bentonite and bimetal decreased nanoscale iron aggregation and increased methyl orange removal efficiency. More than 90 % of methyl orange at 100 mg/L was degraded by B-Fe/Ni (0.15 g/L) in 10 min. By comparison, only 62 % of methyl orange was degraded by B-Fe, and 35 % of methyl orange was degraded by nano-Fe⁰. The degradation rate decreased with the increase of the initial concentration of methyl orange. Lower pH allowed fast removal of methyl orange. Overall our findings show that a nanoscale Fe/Ni on bentonite-supported material is more efficient than nano-Fe⁰. One-step synthesis is more convenient than current two-step-synthesized nanoscale bimetals. Bentonite-supported nanoscale bimetals could therefore be an economic competitive candidate for contaminated water remediation.     

Degradation of chlorinated phenols by nanoscale zero-valent iron

Chlorophenols (CPs), as important contaminants in groundwater, are toxic and difficult to biodegrade. Recently nanoscale zero-valent iron received a great deal of attention because of its excellent performance in treating recalcitrant compounds. In this study, nanoscale zero-valent iron particles were prepared using chemical reduction, and the reductive transformations of three kinds of chlorinated phenols (2-CP, 3-CP, and 4-CP) by nanoscale zero-valent iron under different conditions were investigated. The transformation process of the CPs was shown to be dechlorination first, then cleavage of the benzene ring. The removal efficiency of the CPs varied as follows: 2-CP > 3-CP > 4-CP. The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit (E _LUMO). With the increase in initial concentrations of CPs, removal efficiency decreased a little. But the quantities of CPs reduced increased evidently. Temperature had influence on not only the removal efficiency, but also the transformation pathway. At higher temperatures, dechlorination occurred prior to benzene ring cleavage. At lower temperatures, however, the oxidation product was formed more easily.     

Ag–TiO2 doped photo catalytic degradation of Procion blue H-B dye in textile washwater

The photocatalytic degradation of Procion blue H-B dye in biodegraded textile washwater has been investigated for the complete removal of color and maximum reduction of chemical oxygen demand (COD). Pseudomonas putida was utilized for obtaining biodegraded textile washwater. In this process, silver-doped TiO₂ photocatalyst was prepared and experiments were carried out to study the effects of UV and mercury lamp irradiations on COD reduction and removal of color. The thus prepared silver-doped TiO₂ catalyst was characterized by thermogravimetric and differential thermal analysis, UV-visible spectrometer, X-ray diffraction, scanning electron microscope, energy dispersive X-ray microanalysis, and BET surface area techniques. Adsorption studies were also carried out to evaluate the fitness of isotherm models. The results show that the silver-doped TiO₂ has enhanced the photodegradation of Procion blue H-B dye under UV and mercury lamp irradiations. The enhanced activity of silver-doped TiO₂ is due to the enrichment of electron–hole separation by electron trapping of silver particles.     

Immobilization of NZVI in polydopamine surface-modified biochar for adsorption and degradation of tetracycline in aqueous solution

Polydopamine/NZVI@biochar composite (PDA/NZVI@BC) with high removal efficiency of tetracycline (TC) in aqueous solutions was successfully synthesized. The resultant composite demonstrated high reactivity, excellent stability and reusability over the reaction course. Such excellent performance can be attributed to the presence of the huge surface area on biochar (BC), which could enhance NZVI dispersion and prolong its longevity. The carbonyl group contained on the surface of biochar could combine with the amino group on polydopamine(PDA). The hydroxyl groups in PDA is able to enhance the dispersion and loading of NZVI on BC. Being modified by PDA, the hydrophilicity of biochar was improved. Among BC, pristine NZVI and PDA/NZVI@BC, PDA/ NZVI@BC exhibited the highest activity for removal of TC. Compared with NZVI, the removal efficiency of TC could be increased by 55.9% by using PDA/NZVI@BC under the same conditions. The optimal modification time of PDA was 8h, and the ratio of NZVI to BC was 1:2. In addition, the possible degradation mechanism of TC was proposed, which was based on the analysis of degraded products by LC-MS. Different important factors impacting on TC removal (including mass ratio of NZVI to BC/PDA, initial concentration, pH value and the initial temperature of the solution) were investigated as well. Overall, this study provides a promising alternative material and environmental pollution management option for antibiotic wastewater treatment.

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Simultaneous removal of Co,Cu, and Cr from water by electrocoagulation

This study provides an electrocoagulation process for the removal of metals such as cobalt, copper, and chromium from water using magnesium as anode and galvanized iron as cathode. The various parameters like pH, current density, temperature, and inter electrode distance on the removal efficiency of metals were studied. The results showed that maximum removal efficiency was achieved for cobalt, copper, and chromium with magnesium as anode and galvanized iron as cathode at a current density of 0.025?A?dm^?2 at pH 7.0. First- and second-order rate equations were applied to study adsorption kinetics. The adsorption process follows second-order kinetics model with good correlation. The Langmuir and Freundlich adsorption isotherm models were studied using the experimental data. The Langmuir adsorption isotherm favors monolayer coverage of adsorbed molecules for the adsorption of cobalt, copper, and chromium. Temperature studies showed that adsorption was endothermic and spontaneous in nature.     

Effect of Fe loading quantity on reduction reactivity of nano zero-valent iron supported on chelating resin

In this study, nanoscale zero-valent iron (NZVI) were immobilized within a chelating resin (DOW 3N). To investigate the effect of Fe loading on NZVI reactivity, three NZVI-resin composites with different Fe loading were obtained by preparing Fe(III) solution in 0, 30 and 70% (v/v) ethanol aqueous, respectively; the bromate was used as a model contaminant. TEM reveals that increasing the Fe loading resulted in much larger size and poor dispersion of nanoscale iron particles. The results indicated that the removal efficiency of bromate and the rate constant (K_obs) were decreased with increasing the Fe loading. For the NZVI-resin composite with lower Fe loading, the removal efficiency of bromate declined more significantly with the increase of DO concentrations. Under acidic conditions, decreasing the pH value had the most significant influence on NZVI-R3 with highest Fe loading for bromate removal; however, under alkaline conditions, the most significant influence of pH was on NZVI-R1 with lowest Fe loading. The effects of co-existing anions NO3−, PO43− and HCO3− were also investigated. All of the co-existing anions showed the inhibition to bromate reduction.     

Removal of pentachlorophenol from contaminated soil by catalytic oxidation with iron(III)-porphyrin complexes and potassium monopersulfate

Pentachlorophenol (PCP) in contaminated soil was removed by treatment with aqueous solutions of iron(III)-porphyrin complexes as catalysts and potassium monopersulfate (KHSO₅) as the oxygen donor. The contaminated soils were artificially prepared by spiking PCP to the kaolin and ando soils. Three types of iron(III)-porphyrin complexes, tetra(?p-sulfophenyl) porphineiron(III) (Fe(III)-TPPS), tetra(N-methyl-4-pyridil)porphineiron(III) (Fe(III)-TMPyP) and heme, were examined, and Fe(III)-TPPS was found to be the most effective for removing PCP. Although the sequential addition of KHSO₅ was examined, in an attempt to improve the efficiency of PCP removal, it was not effective. In a preliminary test of various aqueous solutions, the addition of humic acid (HA), with a lower degree of humification, led to a significant enhancement in PCP removal. When HA was added to the soil system, the percentages of PCP removal were increased by up to 10% compared to the absence of HA. Therefore, the addition of HA to the catalytic system was useful in enhancing PCP removal from contaminated soil.     

Metal partitioning in sediment pore water from the Ondo coastal region,Nigeria

Distribution and equilibrium partitioning of metals (Cd, Cu, Cr, Fe, Ni, Pb, Mn, and Zn) between pore water and surface sediments at the Ilaje coast of Ondo State, Nigeria, were studied. The Ilaje River can be one of the interesting research locations because of its economic nature and history of oil pollution. Seasonal variations were observed to investigate possible variations in the availability of metals for organisms throughout the year. The concentrations in both sediments and pore water during the dry and wet seasons were as follows: Cu?>?Fe???Mn?>?Pb?>?Ni?>?Cr?>?Cd?>?Zn. The pore water–sediment partition coefficient (K _p) showed that Zn and Cd were highly mobile while Fe and Cu have restricted mobility. Dissolved organic carbon (DOC) in pore water had a strong influence on mobility and bioavailability of all the metals (p?K _oc), increased levels of Fe and Cu were linked to lithological origin. Concentrations of Pb and Ni were associated with petroleum-related sources. The significance of the field-based techniques for ecotoxicological purposes is discussed.     

Synthesis and antibacterial activity of a Fe3O4–AgCl nanocomposite against Escherichia coli

In this investigation, Fe₃O₄ magnetic nanoparticles (MNPs) were prepared by the alkalinization of an aqueous medium containing ferrous sulfate and ferric chloride. In the next step, a Fe₃O₄–AgCl magnetic nanocomposite was fabricated by the drop-by-drop addition of silver nitrate solution into a NaCl solution containing Fe₃O₄ MNPs. All prepared nanoparticles were characterized by transition electron microscopy (TEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDS). Both particle types varied in size from 2.5 to 20?nm, with an average size of 7.5?nm for Fe₃O₄ MNPs and 12.5?nm for Fe₃O₄–AgCl nanocomposites. The antibacterial effect of the Fe₃O₄ MNPs and fabricated Fe₃O₄–AgCl nanocomposites against Escherichia coli (ATCC 35218) were investigated by conventional serial agar dilution method using the Müller–Hinton Agar medium. The minimum inhibitory concentration was 4?mg?mL^?1 for Fe₃O₄ MNPs and 2?mg?mL^?1 for the Fe₃O₄–AgCl magnetic nanocomposites. Time-kill course assays showed that the Fe₃O₄–AgCl magnetic nanocomposites successfully killed all inoculated bacterial cells during an exposure time of 60?min. The antibacterial activity of recycled Fe₃O₄–AgCl magnetic nanocomposites over four 60?min cycles of antibacterial treatment was further tested against E. coli by the colony-forming unit (CFU) method. The antibacterial efficiency of the nanocomposites was constant over two cycles of antibacterial testing.