Search Results (55)

With increasing energy demands, fuel cells are a popular avenue for portability and low waste emissions. Hydrogen fuel cells are popular due to their potential output power and clean waste. However, due to storage and transport concerns, hydrogen peroxide fuel cells are a promising alternative. Although they have a lower output potential compared to hydrogen fuel cells, peroxide can act as both the oxidizing and reducing agent, simplifying the structure of the cell. In addition to reducing the complexity, hydrogen peroxide is stable in liquid form and can be stored in less demanding methods. This paper investigates chelated metals as electrode material for hydrogen peroxide fuel cells. Chelated metal complexes are ring-like structures that form from binding organic or inorganic compounds with metal ions. They are used in medical imaging, water treatment, and as catalysts for reactions. Copper(II) phthalocyanine, phthalocyanine green, poly(copper phthalocyanine), bis(ethylenediamine)copper(II) hydroxide, iron(III) ferrocyanine, graphene oxide decorated with Fe₃O₄, zinc phthalocyanine, magnesium phthalocyanine, manganese(II) phthalocyanine, cobalt(II) phthalocyanine are investigated as electrode materials for peroxide fuel cells. In this study, the performance of these materials is evaluated using cyclic voltammetry. The voltammograms are compared, as well as observations are made during the materials’ use to measure their effectiveness as electrode material. There has been limited research comparing the use of these chelated metals in the context of hydrogen peroxide fuel cells. Through this research, the goal is to further the viability of hydrogen peroxide fuel cells. Poly(copper phthalocyanine) and graphene oxide doped with iron oxides had strong redox catalytic activity for use in acidic peroxide single-compartment fuel cells, where the poly(copper phthalocyanine) electrode compound generated the highest peak power density of 7.92 mW/cm² and cell output potential of 0.634 V. Full article

Sorbents based on polyacrylonitrile fiber, containing ferrocyanides of transition metals and manganese oxides (CoMn-PAN and FeMn-PAN) or iron(III) hydroxide (CoFe-PAN) in their structure were obtained, as confirmed by the results of X-ray diffraction and energy-dispersive analyses. The selectivity of the obtained sorbents was investigated, along with their ability to sorb Cs, Ba (as an analog of Ra), P, and Be from various natural media, including river water and seawater with varying salinity of 18.2 and 33.8 ‰. The data show that the sorbents are universal for the recovery of artificial ¹³⁷Cs and natural radionuclides from the natural environments, including complex salt composition (seawater). Researching the obtained sorbents during marine expeditions confirmed the efficiency of the obtained materials based on transition metal ferrocyanides and manganese oxides (CoMn-PAN and FeMn-PAN) for the sorption of ¹³⁷Cs, ⁷Be, ²¹⁰Pb, ²¹⁰Po, ²²⁶Ra, ²²⁸Ra, and ²³⁴Th. Additionally, the sorbent based on transition metal ferrocyanides and iron(III) hydroxide (CoFe-PAN) was effective for the sorption of ¹³⁷Cs, ⁷Be, ³²P, ³³P, ²¹⁰Pb, ²¹⁰Po, and ²³⁴Th. Based on the obtained results, methods for comprehensively determining artificial ¹³⁷Cs and natural radionuclides using these sorbents were developed. Full article

Nanofine zero−valent iron (nZVI) is a new, eco−friendly material with strong reducing and adsorbent properties that can be used to clean up heavy metal−affected soils. Herein, nZVI encapsulated with carboxymethyl cellulose (CMC−nZVI) is synthesized via an aqueous−phase reduction technique and subsequently deployed to evaluate its effectiveness in Cr(VI) soil remediation. The characterization analysis used SEM−EDS, XRD, XPS, and LSV to determine the relevant properties of the material. The results show that at an initial Cr(VI) concentration of 169.5 mg·kg⁻¹, 93.2% of Cr(VI) was removed from the soil after 10 h of treatment with CMC−nZVI at pH 3.3. The kinetic analysis showed that CMC−nZVI had the maximum equilibrium adsorption capacity for removing Cr(VI) from soil at 105.3 mg·g⁻¹. This followed a pseudo−second−order kinetic model. The study shows that CMC−nZVI converts Cr(VI) to Cr(III), which forms complexes with Fe(III) ions in the presence of hydroxide ions (OH⁻) to form a highly stable compound that eventually adsorbs into the nanomaterial’s surface for efficient removal. Full article

Graphene oxide and its magnetic nanoparticle-based composites are a well-known tool to remove heavy metals from wastewater. Unfortunately, one of the major issues in handling such small particles consists of their difficult removal from treated wastewater (even when their magnetic properties are exploited), due to their very small diameter. One possible way to overcome this problem is to embed them in a macroscopic biopolymer matrix, such as alginate or chitosan beads. In this way, the adsorbent becomes easier to handle and can be used to build, for example, a packed column, as in a traditional industrial adsorber. In this work, the removal performances of two different embedded magnetic nanocomposite adsorbents (MNAs) are discussed. The first type of MNA is based on ferrite magnetic nanoparticles (MNPs) generated by coprecipitation using iron(II/III) salts and ammonium hydroxide, while the second is based on a 2D material composed of MNP-decorated graphene oxide. Both MNAs were embedded in cross-linked alginate beads and used to treat artificial water contaminated with chromium(III), nickel(II), and copper(II) in different concentrations. The yield of removal and differences between MNAs and non-embedded magnetic nanomaterials are also discussed. From the results, it was found that the time to reach the adsorption equilibrium is higher when compared to that of the nanomaterials only, due to the lower surface/volume ratio of the beads, but the adsorption capacity is higher, due to the additional interaction with alginate. Full article

The mixing of terrestrial groundwater and seawater creates dynamic reaction zones in intertidal areas, where land-derived Fe(II) is oxidized to Fe(III) and then precipitates as Fe hydroxides at the groundwater–seawater interface. These hydrogeochemical processes contribute to the formation of iron bands at the saltwater wedge (SW) and beneath the upper saline plume (USP). This study provides a comprehensive review of physical and geochemical processes at field scale in coastal areas, explores the impact of mineral precipitation on pore structure at pore scale, and synthesizes reactive transport modeling (RTM) approaches for illustrating continuum-scale soil physio-chemical parameters during the evolution of porous media. Upon this review, knowledge gaps and research needs are identified. Additionally, challenges and opportunities are presented. Therefore, we reach the conclusion that the incorporation of observational data into a comprehensive physico-mathematical model becomes imperative for capturing the pore-scale processes in porous media and their influence on groundwater flow and solute transport at large scales. Additionally, a synergistic approach, integrating pore-scale modeling and non-invasive imaging, is equally essential for providing detailed insights into intricate fluid–pore–solid interactions for future studies, as well as facilitating the development of regional engineering-scale models and physio-chemical coupled models with diverse applications in marine science and engineering. Full article

Hematite and goethite are widely occurring chromogenic iron oxides in soils and sediments that are sensitive to climatic dry/wet shifts. However, only by accurately quantifying the content or ratio of hematite and goethite can they be applied reliably to palaeoclimate reconstruction. Compared to the Loess Plateau of China, hematite in the soils of southern China has not been sufficiently studied. We used diffuse reflectance spectroscopy (abbreviation DRS, including the first-derivative curves and the second-derivative curves of the Kubelka–Munk remission functions), combined with ignition at 950 °C, and X-ray fluorescence (XRF) to quantify the hematite content of four tropical-margin iron-rich soil profiles with different matrix compositions in the Leizhou Peninsula, China. We also examined the application of hematite quantification parameters in soils with different matrix compositions under the same climatic conditions. Our main findings are as follows: (i) DRS first-derivative curves can reflect the presence of goethite and hematite in soils, and their relative contents can be compared within the same profile. (ii) The second-derivative curve of the Kubelka–Munk remission functions can reflect the relative proportions of goethite and hematite and provide information about the degree of Al substitution. (iii) Combined with calibration equations, soil redness can reliably quantify the hematite content, but it is necessary to consider the effect of mucilage envelopes in the process of hematite formation. Additionally, we summarize various methods used for quantifying hematite, and the influence of soil matrix compositions, with the aim of providing a reference for hematite quantification elsewhere. We also propose a new indicator (ΔHm_Red/Hm_Red) to help detect iron hydroxide/iron oxide changes in soils. Full article

Two trinuclear oxo-centred iron(III) coordination compounds of monensic and salinomycinic acids (HL) were synthesized and their spectral properties were studied using physicochemical/thermal methods (FT–IR, TG–DTA, TG–MS, EPR, Mössbauer spectroscopy, powder XRD) and elemental analysis. The data suggested the formation of [Fe₃(µ₃–O)L₃(OH)₄] and the probable complex structures were modelled using the DFT method. The computed spectral parameters of the optimized constructs were compared to the experimentally measured ones. In each complex, three metal centres were joined together at the axial position by a μ₃–O unit to form a {Fe₃O}⁷⁺ core. The antibiotics monoanions served as bidentate ligands through the carboxylate and hydroxyl groups located at the termini. The carboxylate moieties played a dual role bridging each two metal centres. Hydroxide anions secured the overall neutral character of the coordination species. Mössbauer spectra displayed asymmetric quadrupole doublets that were consistent with the existence of two types of high-spin iron(III) sites with different environments—two Fe[O₅] and one Fe[O₆] centres. The solid-state EPR studies confirmed the +3 oxidation state of iron with a total spin S_t = 5/2 per trinuclear cluster. The studied complexes are the first iron(III) coordination compounds of monensin and salinomycin reported so far. Full article

The employment of granular ferric iron-(oxy)hydroxides, a well-known economic and effective method, lowers arsenic concentrations in different water types. However, for direct application in polluted groundwaters, there is a need to develop new injectable adsorbents for aquifers that could also neutralize acidic media. In this context, a granular ferric hydroxide-calcite (GFH-C) adsorbent was size-reduced to 0.4–50 µm by sonication with the aim of improving (i) the adsorption of As(III) and As(V) at different pHs and (ii) the pH control through the dissolution of calcite. Batch experiments were conducted to determine As(III) and As(V) adsorption isotherms and kinetics, as well as calcite dissolution kinetics, using GFH-C of two sizes (granular and sonicated). Results showed that the arsenic binding capacity of sonicated adsorbents did not improve significantly. On the contrary, the As(III) and As(V) adsorption kinetics improved with the sonication, as in the case of calcite dissolution kinetics. The dissolution of calcite from the adsorbent made the water pH increase to around 9.2–9.4. The sonicated adsorbent offers an advantage in depolluting As-containing groundwater due to its smaller size, which is linked with faster arsenic adsorption and effective acidic water neutralization. Full article

Higher levels of arsenic (As) and iron (Fe) in groundwater have been reported globally. This study aims to enhance our understanding of the role of naturally occurring dissolved Fe(II) in removing As from groundwater. Field experiments were conducted using five clay filters to investigate As and Fe removal from contaminated groundwater. The field results revealed a wide range of arsenic removal (7.3% to 80%) using the clay filters. The filter with the highest Fe concentration (14.5 mg/L) exhibited the highest As removal, while the lowest Fe concentration (2.2 mg/L) resulted in the lowest percentage of As removal. A direct correlation was observed between effluent As levels and the Fe/As molar ratio. An Fe/As molar ratio of 40 or more was identified as necessary to achieve effluent As concentrations below 50 µg/L. Laboratory batch experiments revealed that Fe(II) was more effective than Fe(III) in removing both As(III) and As(V) from contaminated groundwater. As(V) removal was consistently higher than As(III) removal, regardless of whether Fe(II) or Fe(III) was used. The results suggested that the oxidation of As(III) and the subsequent in situ formation of Fe(III) hydroxide were more efficient in As adsorption than direct Fe(III) treatment. The X-ray absorption fine structure (XAFS) analysis of the floc samples confirmed the dominant peaks of As(V), indicating that most of the As(III) oxidized to As(V) in the As(III)-Fe(II) system. The use of natural Fe(II) in groundwater, possibly supplemented with additional sources of Fe(II), is suggested as a promising, cost-effective, and efficient method for As(III) and As(V) removal. Full article

Long-term production practice proves that good liquor comes out of the old cellar, and the aged pit mud is very important to the quality of Luzhou-flavor liquor. X-ray diffraction, Fourier transform ion cyclotron resonance mass spectrometry, and infrared spectroscopy were used to investigate the composition characteristics of iron-bearing minerals and dissolved organic matter (DOM) in 2-year, 40-year, and 100-year pit mud and yellow soil (raw materials for making pit mud) of Luzhou Laojiao distillery. The results showed that the contents of total iron and crystalline iron minerals decreased significantly, while the ratio of Fe(II)/Fe(III) and the content of amorphous iron (hydr)oxides increased significantly with increasing cellar age. DOM richness, unsaturation, and aromaticity, as well as lignin/phenolics, polyphenols, and polycyclic aromatics ratios, were enhanced in pit mud. The results of the principal component analysis indicate that changes in the morphology and content of iron-bearing minerals in pit mud were significantly correlated with the changes in DOM molecular components, which is mainly attributed to the different affinities of amorphous iron (hydr)oxides and crystalline iron minerals for the DOM components. The study is important for understanding the evolution pattern of iron-bearing minerals and DOM and their interactions during the aging of pit mud and provides a new way to further understand the influence of aged pit mud on Luzhou-flavor liquor production. Full article

The chromium (Cr) limit values are currently tightened to 25 μg L⁻¹ (EU), 5 μg L⁻¹ (Germany), and possibly 10 μg L⁻¹ Cr(VI) (California). The combined process of chemical reduction, coagulation, and biotic filtration (RCbF) efficiently removes Cr(VI) in drinking water. In this study, redox-active substances (O₂, NO₃⁻, Fe²⁺, MnO₂) were investigated concerning their effect on the RCbF process. The experiments were performed at two-stage pilot waterworks for biological iron and manganese removal. O₂ or NO₃⁻ as oxidants affected the RCbF process, neither by consumption of the reductant Fe(II) nor by re-oxidation of already formed Cr(III) in the supernatant of the filter bed. However, the oxidation of Cr(III) by O₂ to Cr(VI) with MnO₂ as a mediator was identified as potential risk for Cr breakthrough. Up to one third of the initial Cr(III) concentration was oxidized to Cr(VI) in the second filter bed within a contact time of only 5 min. The kinetically relevant mechanism seemed to be the formation of Cr(III)Fe(III)-hydroxides and not the reduction of Cr(VI) by Fe(II). Further, the mixing of Cr(VI) containing raw water with Fe(II) containing groundwater was determined as a chemical-free alternative for the RCbF process, depending on the resulting Fe(II) concentration after mixing. Full article

In a contemporary sustainable economy, innovation is a prerequisite to recycling waste into new efficient materials designed to minimize pollution and conserve non-renewable natural resources. Using an innovative approach to remediating metal-polluted water, in this study, eggshell waste was used to prepare two new low-cost nanoadsorbents for the retrieval of nickel from aqueous solutions. Scanning electron microscopy (SEM) results show that in the first eggshell–zeolite (EZ) adsorbent, the zeolite nanoparticles were loaded in the eggshell pores. The preparation for the second (iron(III) oxide-hydroxide)–eggshell–zeolite (FEZ) nanoadsorbent led to double functionalization of the eggshell base with the zeolite nanoparticles, upon simultaneous loading of the pores of the eggshell and zeolite surface with FeOOH particles. Structural modification of the eggshell led to a significant increase in the specific surface, as confirmed using BET analysis. These features enabled the composite EZ and FEZ to remove nickel from aqueous solutions with high performance and adsorption capacities of 321.1 mg/g and 287.9 mg/g, respectively. The results indicate that nickel adsorption on EZ and FEZ is a multimolecular layer, spontaneous, and endothermic process. Concomitantly, the desorption results reflect the high reusability of these two nanomaterials, collectively suggesting the use of waste in the design of new, low-cost, and highly efficient composite nanoadsorbents for environmental bioremediation. Full article

One of the methods of managing sewage sludge (SS) is its soil application. This possibility is promoted by the chemical composition rich in organic matter and nutrients. However, heavy metal contents in SS must meet respective permissible limits. Among the heavy metals in SS, Cu and Zn are found in the largest amount; thus, this study focuses on these elements. The main aim of the study is to investigate the quantitative distribution of metals in sequentially separated fractions of sewage sludge. Additionally, the potential risk of environmental contamination with heavy metals was assessed in the case of SS application for agricultural purposes. The relevant analyses were conducted on four different examples of municipal SS. Based on the total amounts as well as those determined in the SS fractions, the following indices were calculated: I_geo (geoaccumulation index), ICF, (individual contamination factor), and RAC (risk assessment code). The use of data from the sequential analysis as well as the calculated indices made it possible to assess the usefulness of SS in practice in terms of potential introduction of Cu and Zn into the environment with the sludge dose. It was found that total Cu (Cu_tot) and Zn (Zn_tot) did not exceed the permissible limits binding within respective Polish and international regulations. Regardless of the years of study and the analyzed SS, Cu_tot ranged from 260.9 to 393.5 mg·kg⁻¹, and Zn_tot from 475.5 to 1153.1 mg·kg⁻¹. The amounts of Cu and Zn were predominantly reducible (bound to iron and manganese hydroxides, Fr. II) and oxidizable complexes (bound to organic matter and sulfides, Fr. III). The average amounts of Cu in Fr. II ranged from 149.4 to 172.4 mg·kg⁻¹, while those of Zn in Fr. II ranged from 370.9 to 754.6 mg·kg⁻¹. Cu amounts in Fr. III were from 160.9 to 183 mg·kg⁻¹ and Zn amounts in Fr. III were from 104.9 to 171.9 mg·kg⁻¹. Total content of metals as well as TOC values strongly determined the quantitative level of both elements in the SS fractions. Generally, with the increase in the total amount of metals, their levels in the sludge fractions increased. In turn, the increase in TOC resulted in a decrease in the amounts of Cu and Zn in the sludge fractions. Calculated I_geo and ICF ratios showed high and very high SS contamination with Cu and Zn. I_geo values for Cu, regardless of the year of study and sludge sample, that ranged from 4.62 to 5.43 and for Zn from 3.41 to 4.86. At the same time, the ICF values for Cu ranged from 8.59–23.04, and for Zn 15.42–44.47. The RAC values indicated a low (Cu) and medium (Zn) risk of using SS in terms of the potential metal availability in the environment. The RAC values ranged from 1.46 to 4.40% for Cu and from 9.63 to 23.13% for Zn. Full article

To solve radioecological and oceanological problems (estimate the vertical transport, flows of particulate organic carbon, phosphorus biodynamics, submarine groundwater discharge, etc.), it is necessary to determine the natural values of the radionuclides’ activity in seawater and particulate matter. For the first time, the radionuclides’ sorption from seawater was studied using sorbents based on activated carbon modified with iron(III) ferrocyanide (FIC) and based on activated carbon modified with iron(III) hydroxide (FIC A—activated FIC) obtained by FIC sorbent treatment with sodium hydroxide solution. The possibility of trace amounts of phosphorus, beryllium, and cesium recovery in laboratory conditions has been investigated. Distribution coefficients, dynamic, and total dynamic exchange capacities were determined. The physicochemical regularities (isotherm and kinetics) of sorption have been studied. The results obtained are characterized via Langmuir, Freindlich, and Dubinin–Radushkevich isotherm equations, as well as pseudo-first and pseudo-second-order kinetic models, intraparticle diffusion, and the Elovich model. Under expeditionary conditions, the sorption efficiency of ¹³⁷Cs using FIC sorbent, ⁷Be, ³²P, and ³³P—using FIC A sorbent with a single-column method by adding a stable tracer, as well as the sorption efficiency of radionuclides ²¹⁰Pb and ²³⁴Th with their natural content by FIC A sorbent in a two-column mode from large volumes of seawater was assessed. High values of efficiency of their recovery by the studied sorbents were achieved. Full article

For the first time, a comprehensive study of sorbents based on manganese dioxide was carried out for beryllium sorption from seawater in laboratory and expeditionary conditions. The possibility of using several commercially available sorbents based on manganese dioxide (Modix, MDM, DMM, PAN-MnO₂) and phosphorus(V) oxide (PD) for ⁷Be recovery from seawater for solving oceanological problems was evaluated. Beryllium sorption under static and dynamic conditions was studied. The distribution coefficients and dynamic and total dynamic exchange capacities were determined. Sorbents Modix (K_d = (2.2 ± 0.1) × 10³ mL/g) and MDM (K_d = (2.4 ± 0.2) × 10³ mL/g) showed high efficiency. The dependences of the degree of recovery on time (kinetics) and the capacity of the sorbent on the beryllium equilibrium concentration in solution (isotherm) were established. The data obtained were processed using kinetic models (intraparticle diffusion, pseudo-first and pseudo-second orders, Elovich model) and sorption isotherm equations (Langmuir, Freindlich, Dubinin–Radushkevich). The paper contains results of expeditionary studies to evaluate the sorption efficiency of ⁷Be from large volumes of the Black Sea water by various sorbents. We also compared the sorption efficiency of ⁷Be for the considered sorbents with aluminum oxide and previously obtained sorbents based on iron(III) hydroxide. Full article