Metal Binding Mechanism Research Articles

Innovative dual-benefit recycling and sustainable management of municipal solid waste incineration fly ash via ultra-high performance concrete

Millions of tons of municipal solid waste incineration fly ash are generated worldwide each year. Currently, landfilling is the primary disposal method, consuming vast land resources and posing significant risks of soil and groundwater contamination due to the high concentration of hazardous heavy metals. Thus, this study investigated the potential of recycling hazardous municipal solid waste incineration fly ash into non-hazardous ultra-high performance concrete for sustainable development. The mechanisms of heavy metal solidification and binding were examined through Density Functional Theory calculations and microscale experiments. Heavy metals are solidified through the adsorption and binding effects of calcium silicate hydrate and the encapsulation effect of the compact accumulation within the concrete structure. The pore structure of the concrete and the chemical reactions between the fly ash and cement were analyzed to validate the heavy metal solidification mechanism. After solidification, the leaching concentrations of heavy metals from the concrete were two orders of magnitude lower than the limit specified by the Toxicity Characteristic Leaching Procedure. The autogenous shrinking of UHPC with MSWIFA was reduced by about 50 %, and the compressive strength of the concrete decreased. The incorporation of MSWIFA led to approximately a 20 % reduction in energy consumption and carbon emissions. The concrete with MSWIFA exhibited better overall performance. This study presents an innovative and effective approach for recycling municipal solid waste incineration fly ash into non-hazardous concrete, contributing to sustainable hazardous waste management and reducing environmental pollution caused by heavy metals.

Identification and characterization of a rice expansin-like protein with metal-binding properties.

Heavy metal (HM) contamination poses significant threat to agricultural productivity. This study identified and characterized Os09g29690 (OsELP), a rice expansin-like protein. We demonstrated OsELP localizes to the cell wall and is upregulated under various abiotic stresses. Sequence analysis revealed a potential metal-binding CXXXC motif in its conserved domain. Heterologous expression of OsELP in yeast mutants (Δacr3 and Δycf1) enhanced metal tolerance under arsenate [As(V)], arsenite [As(III)], and cadmium [Cd] stress. Yeast cells expressing OsELP accumulated higher amounts of As and Cd, suggesting a potential metal-binding mechanism. This was confirmed through site-directed mutagenesis on the conserved cysteine and serine residues within OsELP. Mutants lacking cysteine residues (mutCS) reduced tolerance to As(III) and Cd but enhanced tolerance to As(V), indicating a role of cysteine in As(III) and Cd binding. Conversely, mutants lacking serine residues (mutSA) reduced tolerance to As(V), suggesting serine's involvement in As(V) binding. These findings reveal the roles of cysteine and serine residues in mediating HM tolerance and binding, confirming OsELP as a key player in HM detoxification through cell wall localization and chelation. This study provides novel insights into the molecular mechanisms of HM tolerance in plants, with potential applications in developing crops with enhanced resistance to HM toxicity.

Heavy metal sorption on struvite recovered from livestock wastewaters and release properties of granular forms.

Phosphorus recovery from wastewater is receiving more attention due to its non-renewable property. As copper (Cu) and zinc (Zn) usually occur in livestock wastewater, this study focused on metal sorption in struvite from swine wastewater and the release properties of granular struvite in solution with varying pH conditions (2, 4, 7). The results demonstrated pH values presented a slightly decreasing trend with increasing Cu/Zn ratio, and Zn exhibited higher sorption performance on struvite crystals than that of Cu. Under the high content of metals in the wastewater, Cu/Zn ratios in the wastewater contributed to varying metal binding forms and mechanisms, resulting in the difference in the leaching properties of nutrients and metal. For the granular struvite manufactured with the adhesion of alginate, the P release percentage achieved 30.3-40.5% after 96h in the wastewater of pH 2, whereas they were only 5.63-8.92% and 1.05-1.50% in the wastewater of pH 4 and 7, respectively. Acid wastewater contributed to the release of two metals, and the release amount of Zn was higher than that of Cu, which is associated with their sorption capacity in crystals. During the latter soil leaching test of adding granular struvite, the NH4+-N and PO43--P concentration in the effluent ranged from 0.34 to 1.26 and 0.62 to 2.56mg/L after 96h, respectively. However, the Cu and Zn could not be measured due to lower than the detection limit under varying treatments. Struvite might be accompanied by quicker metal leaching and slower nutrient leaching when surface sorption dominates in wastewater with lower metal concentrations.

Challenges in geochemical modelling of metal(loid) solubility and binding mechanisms along a soil profile at a multi-contaminated site

Recognising the need for robust models in predicting groundwater contamination risks from metal(loid)s in contaminated topsoil, this study focuses on the geochemical behaviour of As, Cd, Cu, Pb, Sb and Zn in one of Sweden's most heavily contaminated areas. Samples were collected from the waste zone and underlying subsoil down to 5 m and batch experiments were carried out to assess pH-dependent solubility. The results indicate that Cd, Cu, Pb and Zn are efficiently immobilized in the waste zone, while As(V) and Sb(V) are more easily leached. With the exception of Pb and Cu at high pH, the mobilized metals appear to be predominantly in a truly dissolved state, as confirmed by ultrafiltration at 10 kDa.Speciation modelling using Visual MINTEQ did not suggest a significant role of precipitates such as Zn or Pb arsenates and phosphates, although their involvement could not be ruled out. To better understand sorption/desorption patterns, a multi-surface geochemical model was established, drawing on the Stockholm Humic and CD-MUSIC models for organic matter and Fe/Al (hydr)oxide sorption. However, when default parameters were used, the model consistently overestimated the solubility of Cd, Cu, Pb and Zn in both the waste zone and the uncontaminated subsoil. In contrast, As(V) solubility was generally underestimated, also when the reactive surface area of the Fe- and Al (hydr)oxides was decreased in the model. The model's performance was better for Sb(V), though not without imperfections. When the parameters for organic matter were adjusted such that 100% of the solid-phase organic matter was active with respect to ion binding, but only 25% of the dissolved organic matter, the model description improved considerably for Pb and Cu in the upper soil layers. The model revealed distinct differences in the adsorption behaviour of the metal cations, with Pb being sorbed mostly to Fe/Al (hydroxides), whereas a considerable part of Cu was sorbed to organic matter, particularly in the waste zone.Possibly, the dissolution of easily weatherable metal-containing mineral phases may have contributed to the poor model performance for Cd, Zn and for Cu in the deeper soil layers, although other factors, such as a contribution of hydrous SiO2 or Mn oxides to metal binding, could not be ruled out. Metal sorption to carbonate phases may also have been a contributing factor in the waste zone. Lastly, the reactivity of Fe- and Al (hydr)oxides may have been overestimated by oxalate extraction when default parameters for high-surface-area ferrihydrite were applied.These findings provide valuable insights for environmental management and underscore the need for a more detailed characterization of metal(loid) sorption in contaminated soils, as well as the development of improved modelling strategies to enhance solubility predictions.

Functional characterization of rice metallothionein OsMT-I-Id: Insights into metal binding and heavy metal tolerance mechanisms

Metallothioneins (MTs) are cysteine-rich proteins known for their strong metal-binding capabilities, making them effective in detoxifying heavy metals (HMs). This study focuses on characterizing the functional properties of OsMT-I-Id, a type-I Metallothionein found in rice. Using a HM-responsive yeast cup1Δ (DTY4), ycf1∆ (for cadmium), and acr3∆ mutants (for trivalent arsenic), we assessed the impact of OsMT-I-Id on metal accumulation and cellular resilience. Our results demonstrated that yeast cells expressing OsMT-I-Id showed increased tolerance and accumulated higher levels of copper (Cu), arsenic (As), and cadmium (Cd), compared to control cells. This can be attributed to the protein's ability to chelate and bind HMs. Site-directed mutagenesis was employed to investigate the specific contributions of cysteine residues. The study revealed that yeast cells with a mutated C-domain displayed heightened HM sensitivity, while cells with a mutated N-domain exhibited reduced sensitivity. This underscores the critical role of C-cysteine-rich domains in metal binding and tolerance of type-I rice MTs. Furthermore, the study identified the significance of the 12th cysteine position at the N-domain and the 68th and 72nd cysteine positions at the C-domain in influencing OsMT-I-Id metal-binding capacity. This research provides novel insights into the structure-function relationship and metal binding properties of type-I plant MTs.

Heavy Metal Removal from Aqueous Solutions Using Biomaterials and/or Functional Composites: Recent Advances and the Way Forward in Wastewater Treatment Using Digitalization

Due to its low cost, over the past decades, biosorption technology has been extensively carried out to treat heavy metal-laden wastewater using biosorbents. Recent studies on heavy metal biosorption mechanisms and the simulation of mathematical modeling on the biosorption process have enhanced scientific understanding about the binding between target metal cations and the functional group on different surfaces of biomasses as a biosorbent. However, so far, none have provided an overview of mechanistic studies on heavy metal removal from aqueous solutions using inexpensive biosorbents. To close this knowledge gap, this article discusses the applicability of the surface complexation (SC) model for biosorption of a target pollutant. Insightful ideas and directions of future research in wastewater treatment using digital technologies are also presented. It was conclusive from a literature survey of 115 articles (1987–2023) that Aspergillus niger, Penicillium chrysogenum, and Rhizopus nigricans represent biomaterials that have substantial adsorption capacities, up to 200 mg of Au(I)/g, 142 mg of Th/g, and 166 mg of Pb(II)/g, respectively. The metal-binding mechanisms involved include ion exchange, surface complexation, and micro-precipitation. Ion exchange is the only mechanisms that play key roles in sequestering heavy metal using fungal cells with chitin and chitosan. X-ray energy dispersion (XED) and scanning electron microscopy (SEM) analysis were used to evaluate biosorption mechanisms of the inorganic pollutants using physico-chemical characterization on the cell surfaces of the biomass. As metal removal by the biosorbent is affected by its surface properties, surface complexation also occurs. The affinity of the surface complexation depends on the type of functional groups such as phosphate, carboxyl, and amine.

Multinuclear Metal-Binding Ability of the N-Terminal Region of Human Copper Transporter Ctr1: Dependence Upon pH and Metal Oxidation State.

The 14mer peptide corresponding to the N-terminal region of human copper transporter Ctr1 was used to investigate the intricate mechanism of metal binding to this plasma membrane permease responsible for copper import in eukaryotic cells. The peptide contains a high-affinity ATCUN Cu(II)/Ni(II)-selective motif, a methionine-only MxMxxM Cu(I)/Ag(I)-selective motif and a double histidine HH(M) motif, which can bind both Cu(II) and Cu(I)/Ag(I) ions. Using a combination of NMR spectroscopy and electrospray mass spectrometry, clear evidence was gained that the Ctr1 peptide, at neutral pH, can bind one or two metal ions in the same or different oxidation states. Addition of ascorbate to a neutral solution containing Ctr11-14 and Cu(II) in 1:1 ratio does not cause an appreciable reduction of Cu(II) to Cu(I), which is indicative of a tight binding of Cu(II) to the ATCUN motif. However, by lowering the pH to 3.5, the Cu(II) ion detaches from the peptide and becomes susceptible to reduction to Cu(I) by ascorbate. It is noteworthy that at low pH, unlike Cu(II), Cu(I) stably binds to methionines of the peptide. This redox reaction could take place in the lumen of acidic organelles after Ctr1 internalization. Unlike Ctr11-14-Cu(II), bimetallic Ctr11-14-2Cu(II) is susceptible to partial reduction by ascorbate at neutral pH, which is indicative of a lower binding affinity of the second Cu(II) ion. The reduced copper remains bound to the peptide, most likely to the HH(M) motif. By lowering the pH to 3.5, Cu(I) shifts from HH(M) to methionine-only coordination, an indication that only the pH-insensitive methionine motif is competent for metal binding at low pH. The easy interconversion of monovalent cations between different coordination modes was supported by DFT calculations.

Evaluating the Effects of Metal Adduction and Charge Isomerism on Ion-Mobility Measurements using m-Xylene Macrocycles as Models.

Gas-phase ion-mobility spectrometry provides a unique platform to study the effect of mobile charge(s) or charge location on collisional cross section and ion separation. Here, we evaluate the effects of cation/anion adduction in a series of xylene and pyridyl macrocycles that contain ureas and thioureas. We explore how zinc binding led to unexpected deprotonation of the thiourea macrocyclic host in positive polarity ionization and subsequently how charge isomerism due to cation (zinc metal) and anion (chloride counterion) adduction or proton competition among acceptors can affect the measured collisional cross sections in helium and nitrogen buffer gases. Our approach uses synthetic chemistry to design macrocycle targets and a combination of ion-mobility spectrometry mass spectrometry experiments and quantum mechanics calculations to characterize their structural properties. We demonstrate that charge isomerism significantly improves ion-mobility resolution and allows for determination of the metal binding mechanism in metal-inclusion macrocyclic complexes. Additionally, charge isomers can be populated in molecules where individual protons are shared between acceptors. In these cases, interactions via drift gas collisions magnify the conformational differences. Finally, for the macrocyclic systems we report here, charge isomers are observed in both helium and nitrogen drift gases with similar resolution. The separation factor does not simply increase with increasing drift gas polarizability. Our study sheds light on important properties of charge isomerism and offers strategies to take advantage of this phenomenon in analytical separations.

Probing heavy metal binding to phycobiliproteins

Blue‐green algae, also known as cyanobacteria, contain some of the most efficient light‐harvesting complexes known. These large, colourful complexes consist of phycobiliproteins which are extremely valuable in the cosmetics, food, nutraceutical and pharmaceutical industries. Additionally, the colourful and fluorescent properties of phycobiliproteins can be modulated by metal ions, making them highly attractive as heavy metal sensors and heavy metal scavengers. Although the overall quenching ability metal ions have on phycobiliproteins is known, the mechanism of heavy metal binding to phycobiliproteins is not fully understood, limiting their widespread quantitative applications. Here, we show using high‐resolution native mass spectrometry that phycobiliprotein complexes bind metal ions in different manners. Through monitoring the binding equilibria and metal‐binding stoichiometry, we show in particular copper and silver to have drastic, yet different effects on phycobiliprotein structure, both copper and silver modulate the overall complex properties. Together, the data reveals the mechanisms by which metal ions can modulate phycobiliprotein properties which can be used as a basis for the future design of metal‐related phycobiliprotein applications.

Architecture of the two metal-binding sites in prolactin

Metal binding by members of the growth hormone (GH) family of hematopoietic cytokines has been a subject of considerable interest. However, beyond appreciation of its role in reversible packing of GH proteins in secretory granules, the molecular mechanisms of metal binding and granule formation remain poorly understood. Here, we investigate metal binding by a GH family member prolactin (PRL) using paramagnetic metal titration and chelation experiments. Cu2+-mediated paramagnetic relaxation enhancement measurements identified two partial metal-binding sites on the opposite faces of PRL composed of residues H30/H180 and E93/H97, respectively. Coordination of metal ions by these two sites causes formation of inter-molecular bridges between the PRL protomers and enables formation of reversible higher aggregates. These findings in vitro suggest a model for reversible packaging of PRL in secretory granules. The proposed mechanism of metal-promoted PRL aggregation lends insight and support to the previously suggested role of metal coordination in secretory granule formation by GH proteins.

Crystal structure of the metal-free state of glucose isomerase reveals its minimal open configuration for metal binding

Glucose/xylose isomerase catalyzes the reversible isomerization of d-glucose and d-xylose to d-fructose and d-xylulose, respectively. This enzyme is not only involved in sugar metabolism but also has industrial applications, such as in the production of high fructose corn syrup and bioethanol. Various crystal structures of glucose isomerase have shown the binding configuration of the substrate and its molecular mechanism; however, the metal binding mechanism required for the isomerization reaction has not been fully elucidated. To better understand the functional metal binding, the crystal structures of the metal-bound and metal-free states of Streptomyces rubiginosus glucose isomerase (SruGI) were determined at 1.4 Å and 1.5 Å resolution, respectively. In the meal-bound state of SruGI, Mg2+ is bound at the M1 and M2 sites, while in the metal-free state, these sites are occupied by water molecules. Structural comparison between the metal binding sites of the metal-bound and metal-free states of SruGI revealed that residues Glu217 and Asp257 exhibit a rigid configuration at the bottom of the metal binding site, suggesting that they serve as a metal-binding platform that defined the location of the metal. In contrast, the side chains of Glu218, His220, Asp255, Asp257, and Asp287 showed configuration changes such as shifts and rotations. Notably, in the metal-free state, the side chains of these amino acids are shifted away from the metal binding site, indicating that the metal-binding residues exhibit a minimal open configuration, which allows metal binding without large conformational changes.

Investigation of mercury(II) and copper(II) sorption in single and binary systems by alginate/polyethylenimine membranes

This study investigates Hg(II) and Cu(II) sorption in single and binary systems by alginate/polyethylenimine membranes. Batch experiments are conducted to assess the metal sorption performance. FTIR and SEM-EDX analyses are used to identify metal binding mechanism. The sorption kinetics are better fitted by the pseudo-second-order-equation compared to the pseudo-first-order-equation. Three isotherms are compared for fitting the sorption in mono-component solutions and the Sips model gives the best simulation of experimental data. The competitive-Sips model fits well sorption data in Hg-Cu binary solutions and finds that the Cu uptake is drastically reduced by Hg competition. Copper(II) uptake remains negligible at low pH whereas it increases with pH up to 6 because of material deprotonation. Mercury(II) sorption behaves differently, it slightly changes from pH 1 (qeq: 0.76 mmol g−1) to pH 6 (qeq: 0.84 mmol g−1) due to chloro-anion formation. Therefore, playing with the pH allows separating Hg(II) from Cu(II).

Medicinal Au(I) compounds targeting urease as prospective antimicrobial agents: unveiling the structural basis for enzyme inhibition.

A few gold compounds were recently found to show antimicrobial properties in vitro, holding great promise for the discovery of new drugs to overcome antibiotic resistance. Here, the inhibition of the bacterial virulence factor urease by four Au(I)-compounds, namely Au(PEt3)Cl, Au(PEt3)Br, Au(PEt3)I and [Au(PEt3)2]Cl, obtained from the antiarthritic Au(I)-drug Auranofin and earlier reported to act as antimicrobials, is investigated. The three monophosphino Au(I) complexes showed IC50 values in the 30-100 nM range, while the diphosphino Au(I) complex, though being less active, still showed a IC50 value of 7 μM. The structural basis for this inhibition was provided by solving the crystal structures of urease co-crystallized with Au(PEt3)I and [Au(PEt3)2]Cl: at least two Au(I) ions bind the enzyme in a flap domain involved in the catalysis, thus obliterating enzyme activity. Peculiar changes observed in the two structures reveal implications for the mechanism of soft metal binding and enzyme inactivation.

Evaluation of Sequential Extraction Procedure (SEP) to Validate Binding Mechanisms in Soils and Soil-Nano-Calcium Silicate (SNCS) Mixtures

The soils in hazardous waste sites contain heavy metals which would leach into groundwater by various biotic and abiotic processes and eventually pose a threat to human health by contaminating the drinking water. In order to understand pattern of heavy metal leachability, the field conditions can be simulated by adopting various types of sequential extraction methods. In this study, an attempt was made to evaluate the effectiveness and selectivity of a sequential extraction process to determine heavy metal binding mechanisms in soils and soil treated with nano-calcium silicate (NCS). A five-step sequential extraction (SE) procedure was adopted on four soils obtained from a sanitary dumpsite, automobile and battery work units from different localities of Bangalore and a steel plant commissioned at Toranagallu, Bellary, India. The soils were mixed with NCS at varying range of 0.5 to 2% by dry weight of the soil. The NCS-amended soils were spiked with cadmium (Cd2+), nickel (Ni2+) and lead (Pb2+) in concentrations to the tune of 3000 mg/kg. It has been observed that there seems to be a gradual increase in binding ability for the targeted heavy metals when soils were amended with NCS compared to untreated soils. This binding phenomenon was attributed to the presence of exchangeable ions, carbonates, oxides of iron and manganese, organic matter and residual fractions. It was noticed that the residual fractions in soils amended with NCS attenuated maximum quantity of metal ions with Pb2+ at 21.46%, followed by 18.8% for Cd2+ and 9.25% for Ni2+ compared to untreated case. Further, this work highlights the role of residual fraction in enhancing the retention capacity of soils by encapsulation of higher concentrations of contaminants. The current study corroborated the fact that the addition of NCS aids in the better encapsulation of selected heavy metal ions.

Structures of the substrate-binding protein YfeA in apo and zinc-reconstituted holo forms.

In the structural biology of bacterial substrate-binding proteins (SBPs), a growing number of comparisons between substrate-bound and substrate-free forms of metal atom-binding (cluster A-I) SBPs have revealed minimal structural differences between forms. These observations contrast with SBPs that bind substrates such as amino acids or nucleic acids and may undergo >60° rigid-body rotations. Substrate transfer in these SBPs is described by a Venus flytrap model, although this model may not apply to all SBPs. In this report, structures are presented of substrate-free (apo) and reconstituted substrate-bound (holo) YfeA, a polyspecific cluster A-I SBP from Yersinia pestis. It is demonstrated that an apo cluster A-I SBP can be purified by fractionation when co-expressed with its cognate transporter, adding an alternative strategy to the mutagenesis or biochemical treatment used to generate other apo cluster A-I SBPs. The apo YfeA structure contains 111 disordered protein atoms in a mobile helix located in the flexible carboxy-terminal lobe. Metal binding triggers a 15-fold reduction in the solvent-accessible surface area of the metal-binding site and reordering of the 111 protein atoms in the mobile helix. The flexible lobe undergoes a 13.6° rigid-body rotation that is driven by a spring-hammer metal-binding mechanism. This asymmetric rigid-body rotation may be unique to metal atom-binding SBPs (i.e. clusters A-I, A-II and D-IV).

A physicochemical investigation on the metal binding properties of TtSmtB, a thermophilic member of the ArsR/SmtB transcription factor family

The transcription factors of the ArsR/SmtB family are widespread within the bacterial and archaeal kingdoms. They are transcriptional repressors able to sense a variety of metals and undergo allosteric conformational changes upon metal binding, resulting in derepression of genes involved in detoxification. So far, the molecular determinants of specificity, selectivity, and metal binding mechanism have been scarcely investigated in thermophilic microorganisms. TtSmtB, the only ArsR/SmtB member present in the genome of Thermus thermophilus HB27, was chosen as a model to shed light into such molecular mechanisms at high temperature. In the present study, using a multidisciplinary approach, a structural and functional characterization of the protein was performed focusing on its metal interaction and chemical-physical stability. Our data demonstrate that TtSmtB has two distinct metal binding sites per monomer and interacts with di-tri-penta-valent ions with different affinity. Detailed knowledge at molecular level of protein-metal interaction is remarkable to design metal binding domains as scaffolds in metal-based therapies as well as in metal biorecovery or biosensing in the environment.

Metal binding to the dynamic cytoplasmic domain of the cation diffusion facilitator (CDF) protein MamM induces a 'locked-in' configuration.

Cation diffusion facilitator (CDF) proteins are a conserved family of transmembrane transporters that ensure cellular homeostasis of divalent transition metal cations. Metal cations bind to CDF protein's cytoplasmic C-terminal domain (CTD), leading to closure from its apo open V-shaped dimer to a tighter packed structure, followed by a conformational change of the transmembrane domain, thus enabling transport of the metal cation. By implementing a comprehensive range of biochemical and biophysical methods, we studied the molecular mechanism of metal binding to the magnetotactic bacterial CDF protein MamM CTD. Our results reveal that the CTD is rather dynamic in its apo form, and that two dependent metal-binding sites, a single central binding site and two symmetrical, peripheral sites, are available for metal binding. However, only cation binding to the peripheral sites leads to conformational changes that lock the protein in a compact state. Thus, this work reveals how metal binding is regulating the sequential uptakes of metal cations by MamM, and extends our understanding of the complex regulation mechanism of CDF proteins. DATABASE: Structural data are available in RCSB Protein Data Bank under the accession numbers: 6G64, 6G55, 6G5E and 6G6I (for CS, C267S, CS-C267S and W247A, respectively).

Reductive transformations of layered manganese oxides by small organic acids and the fate of trace metals

Abstract Manganese oxides are often major controls on the fate of trace metals in the environment. Exposure to dissolved Mn(II) alters the mineral structure and metal binding mechanisms. Such direct interaction of reduced and oxidized Mn species is largely limited to redox interfaces, but indirect Mn(II) generation may occur more widely. Small organic acids common in soils and organic matter-bearing sediments reduce Mn oxides, generating dissolved Mn(II), but the impact of such reduction on mineral structure and trace metal fate is largely unknown. This study investigates the reaction of three organic acids (oxalate, citrate, and 4-hydroxybenzoate) with two phyllomanganate minerals at pH 4, 5.5, and 7. Aging these phases for four weeks with each organic acid caused partial Mn reduction, generating solid-phase Mn(II) and Mn(III) as well as dissolved Mn(II), with the greatest concentration observed at pH 4. Citrate and 4-hydroxybenzoate produced substantially greater reduction than oxalate, with the net electron transfer indicating that oxidation products of the initial organic acids also reacted with the minerals. In all cases the phyllomanganate sheet structure was preserved after reaction and no phase transformations were observed. Metal uptake was not substantially altered by the organic acids at pH 7, despite these molecules causing substantial solid-phase Mn reduction, whereas at pH 4 adsorption of Ni and Zn decreased compared to organic acid-free systems. Ni adsorption mechanisms transitioned from binding above vacancy sites to at sheet edges in the presence of citrate and 4-hydroxybenzoate, whereas oxalate addition favored Ni binding to vacancy sites. In addition, at pH 7 oxalate and 4-hydroxybenzoate enhanced incorporation into Mn(III)-poor phyllomanganates sheets. For Zn, oxalate had little effect on binding mechanisms but citrate and 4-hydroxybenzoate increased the fraction of tetrahedral species and binding to edge sites. For both metals, changes in uptake and adsorption mechanisms were likely caused by both vacancy filling with Mn(II) and Mn(III) as well as the formation of Mn(III)-rich edges. This study shows that reduction by organic acids alters the reactivity of Mn oxide minerals which enhances trace metal micronutrient and contaminant availability in soils and aquatic systems.

Kinetics Study of The Ability of Compost Material for Removing 〖Cu〗^(2+) from Wastewater

<p>The objective of this study is to examine the ability of a compost material for removing {Cu}^{2+} from aqueous solutions with different parameters using continuous fixed-bed column. Compost was characterized by using Fourier transform infrared spectroscopy which revealed that the metal binding is mainly contributed to the ionic interaction of the metal cations with the carboxyl groups in the hemic substances. Scanning electron microscope images were utilized for morphological analysis of the adsorbent and has revealed that the changes in compost composition could be related to the mechanism of metal binding. Energy dispersive X-ray spectroscopy was used before and after the metal had loaded and gives a good evidence on compost adsorption of {Cu}^{2+} and the metals have its involvement in the interaction in the adsorption process. The influence of the initial {Cu}^{2+}concentration, flow rate, bed heights of the column, and ion exchange have been studied in this research. The adsorption kinetic models have revealed that the behaviour of the {Cu}^{2+\ }adsorption is dependent on rate of concentration, flow rate, and bed heights.</p>

Highly efficient competitive removal of Pb(II) and Ni(II) by chitosan/diatomaceous earth composite

A novel adsorbent for an effective removing of Pb(II) and Ni(II) from aqueous systems in both noncompetitive and competitive modes was prepared by dispersion chitosan onto the diatomaceous earth (CSDE), and then was synthesized into a spherical shape by using a drop-wise method. Its chemical composition, microstructure morphology, and metal-binding mechanism were characterized by dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) techniques. Batch adsorption studies were utilized to evaluate the potential suitability of the prepared CSDE beads and to examine the impact of major adsorption parameters such as solution-pH, initial metal concentration, and contact time on the Pb(II) and Ni(II) adsorption. Under optimal conditions, the maximal adsorption capacities of the CSDE beads based on the Langmuir isotherm model were 175.22 mg/g for Pb(II) and 149.64 mg/g for Ni(II) for noncompetitive adsorption and 234.8 mg/g for both metals in competitive adsorption. The common foreign ions such as Na+, Mg2+, and Ca2+ had insignificant effect on the Pb(II) adsorption while Mg2+ and Ca2+ affected on Ni(II) adsorption. Adsorption kinetics of both metals followed a pseudo-second-order model better than pseudo-first-order model. The prepared CSDE beads could be reused at least ten consecutive adsorption-desorption cycles with marginal decrease in the total adsorption capacity of both metals.