Various types of micropollutants, e.g., pharmaceuticals and their metabolites and resistant strains of pathogenic microorganisms, are usually found in hospital wastewaters. The aim of this paper was to study the presence of 74 frequently used pharmaceuticals, legal and illegal drugs, and antibiotic-resistant bacteria in 5 hospital wastewaters in Slovakia and Czechia and to compare the efficiency of several advanced oxidations processes (AOPs) for sanitation and treatment of such highly polluted wastewaters. The occurrence of micropollutants and antibiotic-resistant bacteria was investigated by in-line SPE-LC-MS/MS technique and cultivation on antibiotic and antibiotic-free selective diagnostic media, respectively. The highest maximum concentrations were found for cotinine (6700 ng/L), bisoprolol (5200 ng/L), metoprolol (2600 ng/L), tramadol (2400 ng/L), sulfamethoxazole (1500 ng/L), and ranitidine (1400 ng/L). In the second part of the study, different advanced oxidation processes, modified Fenton reaction, ferrate(VI), and oxidation by boron-doped diamond electrode were tested in order to eliminate the abovementioned pollutants. Obtained results indicate that the modified Fenton reaction and application of boron-doped diamond electrode were able to eliminate almost the whole spectrum of selected micropollutants with efficiency higher than 90%. All studied methods achieved complete removal of the antibiotic-resistant bacteria present in hospital wastewaters.
- MeSH
- Drug Resistance, Bacterial MeSH
- Boron MeSH
- Water Pollutants, Chemical analysis MeSH
- Chromatography, Liquid MeSH
- Diamond MeSH
- Electrodes MeSH
- Pharmaceutical Preparations analysis MeSH
- Hospitals MeSH
- Waste Disposal, Fluid instrumentation methods MeSH
- Wastewater analysis chemistry microbiology MeSH
- Oxidation-Reduction MeSH
- Hydrogen Peroxide chemistry MeSH
- Tandem Mass Spectrometry MeSH
- Illicit Drugs analysis MeSH
- Medical Waste MeSH
- Iron chemistry MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- Czech Republic MeSH
- Slovakia MeSH
Arsenic compounds are carcinogenic to humans and are typically removed from contaminated water using various sorbents. The ionic composition plays a significant role in arsenate removal efficiency during the process of water remediation. Here, we quantify the effects of natural ions (chlorides, nitrates, carbonates, sulfates, and phosphates) and humic acid on the removal of arsenates by ferrate(VI) at pH = 6.6. In the experiments, the initial concentration of arsenates was 10 mg L-1 (as As) and the concentrations of ions varied in the range from 5 to 100 mg L-1 of element in ionic form and humic acid. The achieved results show that only phosphate ions had principle influence on the efficiency of arsenate removal by ferrate(VI). The effect of phosphates was elucidated by applying transmission electron microscopy, energy-dispersive X-ray spectroscopy, and low temperature in-field 57Fe Mössbauer spectroscopy to solid samples, prepared under different weight ratios of ferrate(VI), arsenates, and phosphates. These results show three crucial effects of phosphates on the arsenate removal mechanisms. At low P:As weight ratio (up to 1:1), the incorporation of arsenate ions into the crystalline structure of γ-Fe2O3/γ-FeOOH nanoparticles was found to be suppressed by the presence of phosphates. Thus, arsenates were mainly adsorbed onto the surface of γ-Fe2O3/γ-FeOOH nanoparticles. Further increase in the P:As weight ratio (more than 1:1) resulted in the competition between arsenates and phosphates sorption. With the increased concentration of phosphate ions, the number of arsenates on the surface of γ-Fe2O3/γ-FeOOH nanoparticles was reduced. Finally, the complexation of iron(III) ions with phosphate ions occurred, leading to a decrease in the arsenates removal efficiency, which resulted from a lower content of precipitated γ-Fe2O3/γ-FeOOH nanoparticles. All these aspects need to be considered prior to application of ferrate(VI) for arsenates removal in real natural waters.
- MeSH
- Adsorption MeSH
- Arsenates chemistry MeSH
- Water Pollutants, Chemical chemistry MeSH
- Chlorides chemistry MeSH
- Water Purification methods MeSH
- Nitrates chemistry MeSH
- Phosphates chemistry MeSH
- Humic Substances * MeSH
- Hydrogen-Ion Concentration MeSH
- Sulfates chemistry MeSH
- Spectroscopy, Mossbauer MeSH
- Carbonates chemistry MeSH
- Ferric Compounds chemistry MeSH
- Iron chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
The presence of iodide (I(-)) in water during disinfection and oxidative treatment of water is a potential health concern because of the formation of iodinated disinfection by-products (DBPs), which may be more toxic than chlorinated DBPs. The kinetics of the oxidation of I(-) by a greener oxidant, ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) was determined as a function of pH. The second-order rate constants (k, M(-1) s(-1)) decreased from 3.9 × 10(4) M(-1) s(-1) at pH 5.0 to 1.2 × 10(1) M(-1) s(-1) at pH 10.3. The kinetics results could be described by the reactivity of monoprotonated species of Fe(VI) (HFe(VI)O4(-)) with I(-). In excess I(-) concentration, triiodide (I3(-)) was formed and the stoichiometry of ∼1:1 ([Fe(VI)]:[I3(-)]) was found in both acidic and basic pH. Ferrate(V) (Fe(V)O4(3-), Fe(V)) and ferrate(IV) (Fe(VI)O4(4-), Fe(IV)) also showed the formation of I3(-) in presence of excess I(-). A mechanism of the formation of I3(-) is proposed, which is consistent with the observed stoichiometry of 1:1. The oxidative treatment of I(-) in water will be rapid (t1/2 = 0.6 s at pH 7.0 using 10 mg L(-1) K2FeO4). The implications of the results and their comparison with the oxidation of I(-) by conventional disinfectants/oxidants in water treatment are briefly discussed.
- MeSH
- Water Pollutants, Chemical analysis chemistry MeSH
- Water Purification methods MeSH
- Disinfectants MeSH
- Halogenation MeSH
- Iodides analysis chemistry MeSH
- Kinetics MeSH
- Oxidation-Reduction MeSH
- Oxidants chemistry MeSH
- Iron chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Research Support, U.S. Gov't, Non-P.H.S. MeSH
The production and use of chlorophenolic compounds in industry has led to the introduction of many xenobiotics, among them chlorophenols (CPs), into the environment. Five CPs are listed in the priority pollutant list of the U.S. EPA, with pentachlorophenol (PCP) even being proposed for listing under the Stockholm Convention as a persistent organic pollutant (POP). A green procedure for degrading such pollutants is greatly needed. The use of ferrate could be such a process. This paper studies the degradation of CPs (with an emphasis on PCP) in the presence of ferrate both in a spiked demineralized water system as well as in real contaminated groundwater. Results proved that ferrate was able to completely remove PCP from both water systems. Investigation of the effect of ferrate purity showed that even less pure and thus much cheaper ferrate was applicable. However, with decreasing ferrate purity, the degradability of CPs may be lower.
Despite the importance of phosphorus as a nutrient for humans and its role in ecological sustainability, its high abundance, resulting in large part from human activities, causes eutrophication that negatively affects the environment and public health. Here, we present the use of ferrate(VI) as an alternative agent for removing phosphorus from aqueous media. We address the mechanism of phosphate removal as a function of the Fe/P mass ratio and the pH value of the solution. The isoelectric point of γ-Fe2O3 nanoparticles, formed as dominant Fe(VI) decomposition products, was identified to play a crucial role in predicting their efficiency in removing of phosphates. Importantly, it was found that the removal efficiency dramatically changes if Fe(VI) is added before (ex-situ conditions) or after (in-situ conditions) the introduction of phosphates into water. Removal under in-situ conditions showed remarkable sorption capacity of 143.4 mg P per gram of ferric precipitates due to better accessibility of active surface sites on in-situ formed ferric oxides/oxyhydroxides. At pH = 6.0-7.0, complete removal of phosphates was observed at a relatively low Fe/P mass ratio (5:1). The results show that phosphates are removed from water solely by sorption on the surface of γ-Fe2O3/γ-FeOOH core/shell nanoparticles. The advantages of Fe(VI) utilization include its environmentally friendly nature, the possibility of easy separation of the final product from water by a magnetic field or by natural settling, and the capacity for successful phosphate elimination at pH values near the neutral range and at low Fe/P mass ratios.
In recent years, particles of iron in higher oxidation states (Fe(IV-VI)), commonly called ferrates, have been presented theoretically as very effective oxidants. They can potentially be used for elimination of a wide range of organic and inorganic contaminants. However, so far the majority of applications have been carried out only as laboratory tests using model samples in many cases. The application of ferrates in remediation programs has so far proved to be more complicated with results failing to meet expectations. Therefore there is a necessity to consider the suitability of their use or consider their possible combination with other agents in order to reach required removal efficiencies in remediation. This study is focused on laboratory experiments using industrial groundwater leading to the proposal of a pilot field application realized as an ex-situ remediation. The combination of ferrates with hydrogen peroxide was used in this study in order to enhance the removal efficiency during pilot remediation of groundwater strongly contaminated by a wide range of organic contaminants. This combination has been shown to be very effective. During the 24-hour reaction time the majority of detected contaminants were removed by approximately 60-80%. Moreover, the unpleasant odor of the water was suppressed and suspended particles were removed by the flocculation effect of ferric sludge.
- MeSH
- Water Pollutants, Chemical chemistry MeSH
- Water Purification methods MeSH
- Laboratories MeSH
- Hydrogen Peroxide chemistry MeSH
- Pilot Projects MeSH
- Groundwater chemistry MeSH
- Environmental Restoration and Remediation methods MeSH
- Iron chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
The removal efficiency of heavy metal ions (cadmium(II), Cd(II); cobalt(II), Co(II); nickel(II), Ni(II); copper(II), Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)) was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective removal of Co(II), Ni(II), and Cu(II) from water was observed at a low Fe-to-heavy metal ion ratio (Fe/M(II) = 2:1) while a removal efficiency of 70% was seen for Cd(II) ions at a high Fe/Cd(II) weight ratio of 15:1. The role of ionic radius and metal valence state was explored by conducting similar removal experiments using Al(III) ions. The unique combination of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), in-field Mössbauer spectroscopy, and magnetization measurements enabled the delineation of several distinct mechanisms for the Fe(VI)-prompted removal of metal ions. Under a Fe/M weight ratio of 5:1, Co(II), Ni(II), and Cu(II) were removed by the formation of MFe2O4 spinel phase and partially through their structural incorporation into octahedral positions of γ-Fe2O3 (maghemite) nanoparticles. In comparison, smaller sized Al(III) ions got incorporated easily into the tetrahedral positions of γ-Fe2O3 nanoparticles. In contrast, Cd(II) ions either did not form the spinel ferrite structure or were not incorporated into the lattic of iron(III) oxide phase due to the distinct electronic structure and ionic radius. Environmentally friendly removal of heavy metal ions at a much smaller dosage of Fe than those of commonly applied iron-containing coagulants and the formation of ferrimagnetic species preventing metal ions leaching back into the environment and allowing their magnetic separation are highlighted.
- MeSH
- Water Pollutants, Chemical chemistry isolation & purification MeSH
- Water Purification methods MeSH
- X-Ray Diffraction MeSH
- Photoelectron Spectroscopy MeSH
- Cations chemistry MeSH
- Hydrogen-Ion Concentration MeSH
- Magnetite Nanoparticles chemistry MeSH
- Potassium Compounds chemistry MeSH
- Iron Compounds chemistry MeSH
- Spectroscopy, Mossbauer MeSH
- Metals, Heavy chemistry isolation & purification MeSH
- Water MeSH
- Ferric Compounds chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
Regarding environmental pollution, the greatest public and scientific concern is aimed at the pollutants listed under the Stockholm Convention. These pollutants are not only persistent but also highly toxic with a high bioaccumulation potential. One of these pollutants, γ-hexachlorocyclohexane (γ-HCH), has been widely used in agriculture, which has resulted in wide dispersion in the environment. Remediation of this persistent and hazardous pollutant is difficult and remains unresolved. Of the many different approaches tested, to date, none has used ferrates. This is unexpected as ferrates are generally believed to be an ideal chemical reagent for water treatment due to their strong oxidation potential and the absence of harmful by-products. In this paper, the degradation/transformation of HCHs by ferrates under laboratory conditions was studied. HCH was degraded during this reaction, producing trichlorobenzenes and pentachlorocyclohexenes as by-products. A detailed investigation of pH conditions during Fe(VI) application identified pH as the main factor affecting degradation. We conclude that ferrate itself is unreactive with HCH and that high pH values, produced by K₂O impurity and the reaction of ferrate with water, are responsible for HCH transformation. Finally, a comparison of Fe(VI) with Fe(0) is provided in order to suggest their environmental applicability for HCH degradation.
- MeSH
- Water Pollutants, Chemical chemistry MeSH
- Water Purification methods MeSH
- Hexachlorocyclohexane chemistry MeSH
- Insecticides chemistry MeSH
- Hydrogen-Ion Concentration MeSH
- Oxidation-Reduction MeSH
- Water chemistry MeSH
- Iron chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
We report the first example of arsenite and arsenate removal from water by incorporation of arsenic into the structure of nanocrystalline iron(III) oxide. Specifically, we show the capability to trap arsenic into the crystal structure of γ-Fe2O3 nanoparticles that are in situ formed during treatment of arsenic-bearing water with ferrate(VI). In water, decomposition of potassium ferrate(VI) yields nanoparticles having core-shell nanoarchitecture with a γ-Fe2O3 core and a γ-FeOOH shell. High-resolution X-ray photoelectron spectroscopy and in-field (57)Fe Mössbauer spectroscopy give unambiguous evidence that a significant portion of arsenic is embedded in the tetrahedral sites of the γ-Fe2O3 spinel structure. Microscopic observations also demonstrate the principal effect of As doping on crystal growth as reflected by considerably reduced average particle size and narrower size distribution of the "in-situ" sample with the embedded arsenic compared to the "ex-situ" sample with arsenic exclusively sorbed on the iron oxide nanoparticle surface. Generally, presented results highlight ferrate(VI) as one of the most promising candidates for advanced technologies of arsenic treatment mainly due to its environmentally friendly character, in situ applicability for treatment of both arsenites and arsenates, and contrary to all known competitive technologies, firmly bound part of arsenic preventing its leaching back to the environment. Moreover, As-containing γ-Fe2O3 nanoparticles are strongly magnetic allowing their separation from the environment by application of an external magnet.
- MeSH
- Arsenic chemistry MeSH
- Arsenates isolation & purification MeSH
- Arsenites isolation & purification MeSH
- Photoelectron Spectroscopy MeSH
- Kinetics MeSH
- Hydrogen-Ion Concentration MeSH
- Crystallography, X-Ray MeSH
- Magnetite Nanoparticles chemistry ultrastructure MeSH
- Spectroscopy, Mossbauer MeSH
- Temperature MeSH
- Particle Size MeSH
- Iron chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
Nanoscale zero-valent iron (nZVI) particles and a composite containing a mixture of ferrate(VI) and ferrate(III) were prepared by thermal procedures. The phase compositions, valence states of iron, and particle sizes of iron-bearing compounds were determined by combination of X-ray powder diffraction, Mössbauer spectroscopy and scanning electron microscopy. The applicability of these environmentally friendly iron based materials in treatment of chemical warfare agents (CWAs) has been tested with three representative compounds, sulfur mustard (bis(2-chlorethyl) sulfide, HD), soman ((3,3'-imethylbutan-2-yl)-methylphosphonofluoridate, GD), and O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothiolate (VX). Zero-valent iron, even in the nanodimensional state, had a sluggish reactivity with CWAs, which was also observed in low degrees of CWAs degradation. On the contrary, ferrate(VI)/(III) composite exhibited a high reactivity and complete degradations of CWAs were accomplished. Under the studied conditions, the estimated first-order rate constants (≈ 10(-2)s(-1)) with the ferrate(VI)/(III) composite were several orders of magnitude higher than those of spontaneous hydrolysis of CWAs (10(-8)-10(-6)s(-1)). The results demonstrated that the oxidative technology based on application of ferrate(VI) is very promising to decontaminate CWAs.
- MeSH
- Chemical Warfare Agents chemistry MeSH
- Water Pollutants, Chemical chemistry MeSH
- Cholinesterase Inhibitors chemistry MeSH
- Water Purification methods MeSH
- X-Ray Diffraction MeSH
- Microscopy, Electron, Scanning MeSH
- Nanoparticles chemistry ultrastructure MeSH
- Organothiophosphorus Compounds chemistry MeSH
- Oxidation-Reduction MeSH
- Powder Diffraction MeSH
- Soman chemistry MeSH
- Mustard Gas chemistry MeSH
- Iron chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
