Chelator Concentration Research Articles

Selective extraction of lead from chelator-rich effluents using a biomass-based sorbent

The efficient removal of lead (Pb) from waste streams containing chelators presents a significant challenge due to the high stability and mobility of Pb-chelator complexes. This study investigates a novel approach utilizing a biomass-based sorbent, proline-incorporated dithiocarbamate-modified cellulose with epoxy-cross-linkage (DMC-Pro-Epo6), to extract Pb from effluents with excess chelators. DMC-Pro-Epo6 exhibited exceptional Pb(II) sorption performance under controlled and various chelator-rich conditions. The sorbent maintained high sorption efficiency even with 100-fold excess chelator concentration and competing metal ions. DMC-Pro-Epo6 also outperformed commercially-available ion-selective sorbents in terms of separation efficiency. The sorption kinetics followed a pseudo-second order model, demonstrating rapid sorption with equilibrium reached within 20 min. The maximum sorption capacities of DMC-Pro-Epo6 obtained from the Langmuir isotherm model were 1267 and 659 µmol g−1 in Pb(II)-containing aqueous solution and Pb(II)-containing EDTA solution, respectively. X-ray photoelectron and absorption spectroscopy analyses, along with sorption parameters, confirmed a chemisorption mechanism for Pb(II) sorption onto DMC-Pro-Epo6. Validation of the protocol using real waste samples with complex chelator and base metal ion matrices resulted in a quantitative and selective extraction of 92 to 99 % of Pb(II). This success suggests the potential for scaling up the developed process. Compared to conventional treatment methods, the proposed technique offers a more efficient and streamlined process for separating metal ions and chelators from effluents.

Remediation of fluoride-contaminated wastes: Chelator-assisted washing and subsequent immobilization using CaO and H3PO4

Fluoride (F) contamination in industrial waste is a significant challenge for sustainable materials recycling. Existing techniques for mitigating F contamination focus on immobilization, converting F compounds to insoluble forms while leaving the total F content untreated. Chelator-assisted washing is considered a promising alternative remediation strategy that can indirectly release F by entrapping and dissolving F-bearing minerals. This study evaluates the effectiveness of chelator-assisted washing in removing F from three real F-contaminated waste samples (TCS-49, TCS-51, and TCS-52) by treating with four different chelators, ethylenediaminetetraacetic acid (EDTA), ethylenediamine N,N′-disuccinic acid (EDDS), diethylenetriaminepentaacetic acid (DTPA), and 3-hydroxy-2,2′-imino disuccinic acid (HIDS). The influence of key washing variables, including chelator type, solution pH, chelator concentration, washing time, and liquid-to-solid (L/S) ratio toward F extraction was assessed and optimized for attaining the maximum extraction. All chelators exhibited the highest F extraction from TCS-49 and TCS-51 at pH 11, whereas in TCS-52 it showed a discrete extraction pattern. Under optimized conditions (concentration, 10 mmol L−1; pH, 11; washing duration, 3 h; and L/S ratio, 10:1), EDTA outperformed the other chelators, enhancing F extraction by 2.1 and 1.2 times for TCS-49 and TCS-51, respectively, compared with those of control treatments. However, for TCS-52, the efficiency of EDTA was analogous to that of the control under the same washing conditions. The linear correlation between the extracted F and F-containing minerals suggests that the chelator-induced F removal from contaminated waste involves the entrapment and dissolution of F-bearing minerals, especially Ca and Fe. The subsequent post-washing immobilization of chelator-washed waste residues using CaO or H3PO4 significantly reduced the content of leachable F under the regulatory limit.

Removal of Metal from Carboxypeptidase A Proceeds via a Split Pathway: Implications for the General Mechanisms of Metalloenzyme Inactivation by Chelating Agents.

The chelation of protein-bound metal ions is typically thought to follow either a dissociative (D) or an associative (A) path. While the former mechanism involves the spontaneous dissociation of the metal from the protein prior to chelation, the latter route is characterized by the formation of an intermediate protein-metal-chelator ternary complex. Using the prototypical zinc protease carboxypeptidase A (CPA) and a variety of charged and neutral chelating agents, we demonstrate that inactivation of the enzyme (and likely other metalloproteins) proceeds through a split pathway with contributions from both D- and A-type mechanisms. In the case of charged chelators such as ethylenediaminetetraacetic acid (EDTA), the proportions of both paths could be tuned over a wide range through variation of the chelator concentration and the ionic strength, I (from ∼95% A type at low I values to ∼5% at high I values). By measuring the EDTA concentration and time dependence of CPA inactivation and fitting the obtained kinetic data to a modified time-dependent inhibition model, we obtained the rate constants for the A and D paths (kinact and koff, respectively) and the inhibition constant (KI) for the formation of the CPA-Zn2+-EDTA ternary complex, indicating that the decreased contribution of the A-type mechanism at high ionic strengths originates from a large (40-fold; at I = 0.5 M) increase in KI. This observation might be related to a triarginine motif in CPA that electrostatically steers negatively charged substrates into the active site and may therefore also guide carboxylate-bearing chelators toward the Zn2+ ion.

Preclinical evaluation of MC1R targeting theranostic pair [155Tb]Tb-crown-αMSH and [161Tb]Tb-crown-αMSH

BackgroundTargeted radionuclide therapy is established as a highly effective strategy for the treatment of metastatic tumors; however, the co-development of suitable imaging companions to therapy remains significant challenge. Theranostic isotopes of terbium (149Tb, 152Tb, 155Tb, 161Tb) have the potential to provide chemically identical radionuclidic pairs, which collectively encompass all modes of nuclear decay relevant to nuclear medicine. Herein, we report the first radiochemistry and preclinical studies involving 155Tb- and 161Tb-labeled crown-αMSH, a small peptide-based bioconjugate suitable for targeting melanoma. Methods155Tb was produced via proton induced spallation of Ta targets using the isotope separation and acceleration facility at TRIUMF with isotope separation on-line (ISAC/ISOL). The radiolabeling characteristics of crown-αMSH with 155Tb and/or 161Tb were evaluated by concentration-dependence radiolabeling studies, and radio-HPLC stability studies. LogD7.4 measurements were obtained for [161Tb]Tb-crown-αMSH. Competitive binding assays were undertaken to determine the inhibition constant for [natTb]Tb-crown-αMSH in B16-F10 cells. Pre-clinical biodistribution and SPECT/CT imaging studies of 155Tb and 161Tb labeled crown-αMSH were undertaken in male C57Bl/6 J mice bearing B16-F10 melanoma tumors to evaluate tumor specific uptake and imaging potential for each radionuclide. ResultsQuantitative radiolabeling of crown-αMSH with [155Tb]Tb3+ and [161Tb]Tb3+ was demonstrated under mild conditions (RT, 10 min) and low chelator concentrations; achieving high molar activities (23–29 MBq/nmol). Radio-HPLC studies showed [161Tb]Tb-crown-αMSH maintains excellent radiochemical purity in human serum, while gradual metabolic degradation is observed in mouse serum. Competitive binding assays showed the high affinity of [natTb]Tb-crown-αMSH toward MC1R. Two different methods for preparation of the [155Tb]Tb-crown-αMSH radiotracer were investigated and the impacts on the biodistribution profile in tumor bearing mice is compared. Preclinical in vivo studies of 155Tb- and 161Tb- labeled crown-αMSH were performed in parallel, in mice bearing B16-F10 tumors; where the biodistribution results showed similar tumor specific uptake (6.06–7.44 %IA/g at 2 h pi) and very low uptake in nontarget organs. These results were further corroborated through a series of single-photon emission computed tomography (SPECT) studies, with [155Tb]Tb-crown-αMSH and [161Tb]Tb-crown-αMSH showing comparable uptake profiles and excellent image contrast. ConclusionsCollectively, our studies highlight the promising characteristics of [155Tb]Tb-crown-αMSH and [161Tb]Tb-crown-αMSH as theranostic pair for nuclear imaging (155Tb) and radionuclide therapy (161Tb).

Iron overload promotes hemochromatosis-associated osteoarthritis via the mTORC1-p70S6K/4E-BP1 pathway

BackgroundsJoint iron overload in hemochromatosis induces M1 polarization in synovial macrophages, releasing pro-inflammatory factors and leading to osteoarthritis development. However, the mechanism by which iron overload regulates M1 polarization remains unclear. This study aims to elucidate the mechanism by which synovial iron overload promotes macrophage M1 polarization. MethodsIn vitro, RAW264.7 macrophages were treated with iron and divided into five groups based on the concentration of the iron chelator, desferrioxamine (DFO): Ctrl, Fe, DFO1, DFO2, and DFO3. In vivo, rats were categorized into five groups based on iron overload and intra-articular DFO injection: A-Ctrl, A-Fe, A-DFO1, A-DFO2, and A-DFO3. Osteoarthritis was induced by transecting the left knee anterior cruciate ligament. Macrophage morphology was observed; Prussian Blue staining quantified iron deposition in macrophages, synovium, and liver; serum iron concentration was measured using the ferrozine method; cartilage damage was assessed using H&E and Safranin O-Fast Green staining; qPCR detected iNOS and Arg-1 expression; Western Blot analyzed the protein expression of iNOS, Arg-1, 4E-BP1, phosphorylated 4E-BP1, p70S6K, and phosphorylated p70S6K; ELISA measured TNF-α and IL-6 concentrations in supernatants; and immunohistochemistry examined the protein expression of F4/80, iNOS, Arg-1, 4E-BP1, phosphorylated 4E-BP1, p70S6K, and phosphorylated p70S6K in the synovium. ResultsIn vitro, iron-treated macrophages exhibited Prussian Blue staining indicative of iron overload and morphological changes towards M1 polarization. qPCR and Western Blot revealed increased expression of the M1 polarization markers iNOS and its protein. ELISA showed elevated TNF-α and IL-6 levels in supernatants. In vivo, ferrozine assay indicated significantly increased serum iron concentrations in all groups except A-Ctrl; Prussian Blue staining showed increased liver iron deposition in all groups except A-Ctrl. Iron deposition in rat synovium decreased in a DFO concentration-dependent manner; immunohistochemistry showed a corresponding decrease in iNOS and phosphorylated 4E-BP1 expression, and an increase in Arg-1 expression. ConclusionIntracellular iron overload may exacerbate joint cartilage damage by promoting synovial macrophage M1 polarization through phosphorylation of 4E-BP1 in the mTORC1-p70S6K/4E-BP1 pathway.

Remediation of cadmium-contaminated soil: GLDA-assisted extraction and sequential FeCl3–CaO-based post-stabilization

Cadmium (Cd) contamination of farmland soils is a growing concern because of its highly toxic impact on ecosystems and human health. Chelator-assisted washing and chemical immobilization are effective remediation strategies for Cd-contaminated soils. Ethylenediaminetetraacetic acid (EDTA) has traditionally been used for soil washing, but its persistence in the environment and subsequent toxicity have raised significant ecological concerns. Consequently, biodegradable chelators have gained increasing attention as eco-friendly alternatives to the persistent chelator, EDTA. Therefore, this study evaluated the performance and efficacy of three biodegradable chelators: L-glutamate-N,N′-diacetic acid (GLDA), methylglycine-diacetic acid (MGDA), and 3-hydroxy-2,2′-iminodisuccinic acid (HIDS) in comparison to EDTA for remediating a real Cd-contaminated agricultural soil. The influence of treatment parameters, including chelator variants, washing time, chelator concentration, solution pH, and liquid-to-soil ratio (L/S) on Cd extraction was studied and optimized to attain the maximum removal rate. Following chelator-assisted washing, the efficacy of a stabilization preference combining FeCl3 and CaO in reducing the leaching potential of residual Cd in chelator-washed soil residues was also investigated. GLDA demonstrated comparable Cd extraction efficiency to EDTA, and the Cd extraction efficiency was found to be positively correlated with the soil washing parameters. However, under the optimized conditions (chelator concentration: 10 mmol L−1; washing time: 3 h; solution pH: 3; L/S ratio: 10:1), GLDA exhibited a higher Cd extraction rate than EDTA or the other chelators. Furthermore, a post-treatment process incorporating FeCl3 and CaO substantially diminished the water-leachable Cd content in the resultant soil residues. The proposed remediation strategy, which combines chemically assisted washing and stabilization, could be a practical option for extracting bulk Cd from soil and reducing the leaching potential of residual Cd.

A ribonuclease activity linked to DYW1 in vitro is inhibited by RIP/MORF proteins

Organellar C-to-U RNA editing in plants occurs in complexes composed of various classes of nuclear-encoded proteins. DYW-deaminases are zinc metalloenzymes that catalyze hydrolytic deamination required for C-to-U modification editing. Solved crystal structures for DYW-deaminase domains display all structural features consistent with a canonical cytidine deamination mechanism. However, some recombinant DYW-deaminases from plants have been associated with ribonuclease activity in vitro. Direct ribonuclease activity by an editing factor is confounding since it is not required for deamination of cytosine, theoretically would be inimical for mRNA editing, and does not have a clear physiological function in vivo. His-tagged recombinant DYW1 from Arabidopsis thaliana (rAtDYW1) was expressed and purified using immobilized metal affinity chromatography (IMAC). Fluorescently labeled RNA oligonucleotides were incubated with recombinant AtDYW1 under different conditions. Percent relative cleavage of RNA probes was recorded at multiple time points from triplicate reactions. The effects of treatment with zinc chelators EDTA and 1, 10-phenanthroline were examined for rAtDYW1. Recombinant His-tagged RNA editing factors AtRIP2, ZmRIP9, AtRIP9, AtOZ1, AtCRR4, and AtORRM1 were expressed in E. coli and purified. Ribonuclease activity was assayed for rAtDYW1 in the presence of different editing factors. Lastly, the effects on nuclease activity in the presence of nucleotides and modified nucleosides were investigated. RNA cleavage observed in this study was linked to the recombinant editing factor rAtDYW1 in vitro. The cleavage reaction is sensitive to high concentrations of zinc chelators, indicating a role for zinc ions for activity. The addition of equal molar concentrations of recombinant RIP/MORF proteins reduced cleavage activity associated with rAtDYW1. However, addition of equal molar concentrations of purified recombinant editing complex proteins AtCRR4, AtORRM1, and AtOZ1 did not strongly inhibit ribonuclease activity on RNAs lacking an AtCRR4 cis-element. Though AtCRR4 inhibited AtDYW1 activity for oligonucleotides with a cognate cis-element. The observation that editing factors limit ribonuclease activity of rAtDYW1 in vitro, suggests that nuclease activities are limited to RNAs in absence of native editing complex partners. Purified rAtDYW1 was associated with the hydrolysis of RNA in vitro, and activity was specifically inhibited by RNA editing factors.

The novel extraordinary separation and preconcentration approach for Cd2+: “Hydrophobic Immiscible Chelating Fluid” based micro-extraction

The novel, extraordinary and highly selective separation and preconcentration approach based on hydrophobic immiscible chelating fluid (HICF) having superior features (simultaneous chelation, extraction and masking) and combined with automatized syringe discharge system by peristaltic pump was established firstly for simultaneous chelation and micro-extraction of Cd2+. Mixture of tetra butyl ammonium iodide, tetra butyl ammonium fluoride, n-pentanol (1:1:10) and dithizone were used to formulate HICF. The parameters including pH, chelator concentration on both characteristic of HICF and extraction of Cd2+, time of vortex mixing, amount of HICF and sample volume were optimized and investigated in detail. The optimized method has permitted to obtain 25 preconcentration factor (PF) and detect the lowest cadmium concentration having 2.1 µg L−1 (LOD) in the aqueous solution. Interference effect of defiant metal cations was investigated in detail. The dynamic range of the method (LDR) was obtained linearly between 7.2 and 1500 µg L−1. Relative standard deviations (% RSD) were below than % 4.2 throughout the experiments. The envisaged possible extraction mechanisms were explained. The proposed novel method was validated with applications of multiple analyte-addition recovery tests in water samples (tap, lake and natural spring water) and analysis of standard reference material (UME EnvCRM 03 Elements in Soil). Quantitative satisfactory recovery values changing between 98 and 106 % were obtained. Validated method was also applied to determine Cd contents of sediment, mushroom and raw tobacco samples. The main advantage of HICF is that it contains masking and chelating agents and extraction solvent in only one liquid. Therefore, possible concentration and volume errors were minimized by single micropipette injection that ensured time saving and simplicity for applicability of the method by the analysts. Moreover, automated syringe discharge system has provided repeatable and precision extraction results.

Washing Bottom Sediment for The Removal of Arsenic from Contaminated Italian Coast

Among various forms of anthropogenic pollution, the release of toxic metals in the environment is a global concern due to the high toxicity of these metals towards living organisms. In the last 20 years, sediment washing has gained increasing attention thanks to its capability to remove toxic metals from contaminated matrices. In this paper, we propose a Response Surface Methodology method for the washing of selected marine sediments of the Bagnoli-Coroglio Bay (Campania region, Italy) polluted with arsenic and other contaminants. We focused our attention on different factors affecting the clean-up performance (i.e., liquid/solid ratio, chelating concentration, and reaction time). The highest As removal efficiency (i.e., >30 μg/g) was obtained at a liquid/solid ratio of 10:1 (v/w), a citric acid concentration of 1000 mM, and a washing time of 94.22 h. Based on these optimum results, ecotoxicological tests were performed and evaluated in two marine model species (i.e., Phaeodactylum tricornutum and Aliivibrio fischeri), which were exposed to the washing solutions. Reduced inhibition of the model species was observed after nutrient addition. Overall, this study provides an effective tool to quickly assess the optimum operating conditions to be set during the washing procedures of a broad range of marine sediments with similar physicochemical properties (i.e., grain size and type of pollution).

Removal of Ferrous using Citric Acid in Patchouli Oil Purification by Complexometry

This study is aimed to examine citric acids as a potential chelating agent to decrease colloidal impurities in patchouli oil to improve its quality. It covers colour, specific density, refractive index, acid value, iron content, oleoresin oil content, and patchouli alcohol. Complete Randomized Design with factorial design is used with two factors and repeated 3 times. Factors are (1) citric acid concentration consists of 0.25%, 0.5%, 1.0% and 1.50% (w/v), (2) stirring time of 30, 60 and 90 minutes. Further, purified oil by citric acid was compared to purified oil by Ethylene Diamine Tetra Acetate (EDTA). Findings show that the concentration of chelating agents and the time of stirring have an effect on the quality of patchouli oil. The higher the chelating concentration and the more the stirring time, the better the quality of purified patchouli oil in terms of colour, specific density, refractive index, acid value, and iron content. Findings also show that citric acid has almost the same performance as EDTA. The main components in patchouli oil (patchouli alcohol and oleoresin oil) are not affected by treatment. Purified patchouli oil by using citric acid meets Indonesian National Standard (SNI) requirements so citric acid is one of the potential chelating agents.

Modern Developments in Bifunctional Chelator Design for Gallium Radiopharmaceuticals.

The positron-emitting radionuclide gallium-68 has become increasingly utilised in both preclinical and clinical settings with positron emission tomography (PET). The synthesis of radiochemically pure gallium-68 radiopharmaceuticals relies on careful consideration of the coordination chemistry. The short half-life of 68 min necessitates rapid quantitative radiolabelling (≤10 min). Desirable radiolabelling conditions include near-neutral pH, ambient temperatures, and low chelator concentrations to achieve the desired apparent molar activity. This review presents a broad overview of the requirements of an efficient bifunctional chelator in relation to the aqueous coordination chemistry of gallium. Developments in bifunctional chelator design and application are then presented and grouped according to eight categories of bifunctional chelator: the macrocyclic chelators DOTA and TACN; the acyclic HBED, pyridinecarboxylates, siderophores, tris(hydroxypyridinones), and DTPA; and the mesocyclic diazepines.

Iron restriction induces the small-colony variant phenotype in Staphylococcus aureus.

Pathogens such as Staphylococcus aureus must overcome host-induced selective pressures, including limited iron availability. To cope with the harsh conditions of the host environment, S. aureus can adapt its physiology in multiple ways. One of these adaptations is the fermenting small-colony variant (SCV) phenotype, which is known to be inherently tolerant to certain classes of antibiotics and heme toxicity. We hypothesized that SCVs might also behave uniquely in response to iron starvation since one of the major cellular uses of iron is the respiration machinery. In this study, a respiring strain of S. aureus and fermenting SCV strains were treated with different concentrations of the iron chelator, 2,2' dipyridyl (DIP). Our data demonstrate that a major impact of iron starvation in S. aureus is the repression of respiration and the induction of the SCV phenotype. We demonstrate that the SCV phenotype transiently induced by iron starvation mimics the aminoglycoside recalcitrance exhibited by genetic SCVs. Furthermore, prolonged growth in iron starvation promotes increased emergence of stable aminoglycoside-resistant SCVs relative to the naturally occurring subpopulation of SCVs within an S. aureus community. These findings may have relevance to physiological and evolutionary processes occurring within bacterial populations infecting iron-limited host environments.

Loss of LEUCINE CARBOXYL METHYLTRANSFERASE 1 interferes with metal homeostasis in Arabidopsis and enhances susceptibility to environmental stresses

The biochemical function of LEUCINE CARBOXYL METHYLTRANSFERASE 1 (LCMT1) is to transfer a methyl group from the methyl donor S-adenosylmethionine (SAM) to the catalytic subunits of PROTEIN PHOSPHATASE 2A (PP2Ac), PP4 and PP6. This post-translational modification by LCMT1 is found throughout eukaryotes from yeast to animals and plants, indicating that its function is essential. However, Arabidopsis with knocked out LCMT1 still grows and develops almost normally, at least under optimal growth conditions. We therefore proposed that the presence of LCMT1 would be important under non-optimal growth conditions and favoured plant survival during evolution. To shed light on the physiological functions of plant LCMT1, phenotypes of the lcmt1 mutant and wild type Arabidopsis were compared under various conditions including exposure to heavy metals, variable chelator concentrations, and increased temperature. The lcmt1 mutant was found to be more susceptible to these environmental changes than wild type and resulted in poor growth of seedlings and rosette stage plants. Element analysis of rosette stage plants mainly showed a difference between the lcmt1 mutant and wild type regarding concentrations of sodium and boron, two-fold up or halved, respectively. In both lcmt1 and wild type, lack of EDTA in the growth medium resulted in enhanced concentration of copper, manganese, zinc and sulphur, and especially lcmt1 growth was hampered by these conditions. The altered phenotype in response to stress, the element and mRNA transcript analysis substantiate that LCMT1 has an important role in metal homeostasis and show that functional LCMT1 is necessary to prevent damages from heat, heavy metals or lack of chelator.

Development of a blood calcium test for hypocalcemia diagnosis in dairy cows

Hypocalcemia, defined as total blood calcium concentrations below 2.1 mM, has detrimental impacts on welfare, production and reproduction in dairy cattle. Yet, no cow-side test exists for testing total bovine blood calcium. Here, we modified the split trehalase complementation assay to detect total calcium in serum by incorporating calmodulin and the M13 peptide as fusion partners to the trehalase fragments. In the presence of calcium, calmodulin undergoes a conformation change and gains strong affinity for M13 peptide. A high reactive assay for calcium was developed with detection threshold of 10 uM and dynamic range between 1 uM and 1 mM. The addition of a specific concentration of calcium chelator, EDTA, in mild acidic conditions, shifted the dynamic range to physiological calcium concentrations and transformed the sensor from ionized calcium sensor to total calcium sensor. The sensor was validated on a collection of 213 bovine serum samples by comparison with quantitative colorimetric calcium test. A correlation coefficient of 0.81 was achieved and the accuracy of detecting subclinical hypocalcemia was 0.86 and specificity of 100%. The area under the Receiver Operating Characteristic curve was 0.93. The concordance correlation coefficient (0.80), Bland-Altman plot and weighted Kappa coefficient (0.71) demonstrated a substantial agreement between both methods. In conclusion, a novel total calcium test was developed that can be used as a convenient high throughput laboratory test and with potential to be incorporated into a version compatible with on-farm testing.

Biodegradable chelant-metal complexes enhance cadmium phytoextraction efficiency of Solanum americanum.

Toxic contaminants (metals and metal-containing compounds) are accumulating in the environment at an astonishing rate and jeopardize human health. Remarkable industrial revolution and the spectacular economic growth are the prime causes for the release of such toxic contaminants in the environment. Cadmium (Cd) is ranked the 7th most toxic compound by the Agency for Toxic Substances and Disease Registry (USA), owing to its high carcinogenicity and non-biodegradability even at miniscule concentration. The present study assessed the efficiency of four biodegradable chelants [nitrilotriacetic acid (NTA), ethylenediamine disuccinate (EDDS), ethylene glycol tetraacetic acid (EGTA), and citric acid (CA)] and their dose (5mM and 10mM) in enhancing metal accumulation in Solanum americanum Mill. (grown under 24mg Cd kg-1 soil) through morpho-physiological and metal extraction parameters. Significant variations were observed for most of the studied parameters in response to chelants and their doses. However, ratio of root and shoot length, and plant height stress tolerance index differed non-significantly. The potential of chelants to enhance Cd removal efficiency was in the order - EGTA (7.44%) > EDDS (6.05%) > NTA (4.12%) > CA (2.75%). EGTA and EDDS exhibited dose-dependent behavior for Cd extraction with 10mM dose being more efficient than 5mM dose. Structural equation model (SEM) depicted strong positive interaction of metal extraction parameters with chelants (Z-value = 11.61, p = 0.001). This study provides insights into the importance of selecting appropriate dose of biodegradable chelants for Cd extraction, as high chelant concentration might also result in phytotoxicity. In the future, phytoextraction potential of these chelants needs to be examined through field studies under natural environmental conditions.

Enhanced remediation of arsenic-contaminated excavated soil using a binary blend of biodegradable surfactant and chelator

The reclamation of geogenic As-contaminated excavated soils as construction additives can reduce the post-disposal impact on the ecosystem and space. Although retaining soil characteristics while reducing contaminant load is a challenging task, washing remediation with biodegradable surfactants or chelators is a promising alternative to non-biodegradable counterparts. In this study, newly synthesized biodegradable surfactants (SDG: sodium N-dodecanoyl-glycinate, SDBA: sodium N-dodecanoyl-β-alaninate, SDGBH: sodium N-dodecanoyl-α,γ-glutamyl-bis-hydroxyprolinate, SDT: sodium N-dodecanoyl-taurinate, and DCPC: N-dodecyl-3-carbamoyl-pyridinium-chloride) and biodegradable chelators (EDDS: ethylenediamine N,N’-disuccinic acid, GLDA: L-glutamate-N, N’-diacetic acid, and HIDS: 3-hydroxy-2,2′-imino disuccinic acid) are evaluated for the remediation of As-contaminated soil. The operating variables, such as washing duration, solution pH, and surfactant or chelator concentration, are optimized for maximum As extraction. SDT shows the highest As-extraction efficiency irrespective of solution pH and surfactant variants, while HIDS is the superior chelator under acidic or alkaline conditions. A binary blend of SDT and HIDS is evaluated for As extraction under varying operating conditions. The SDT–HIDS binary blend demonstrates 6.9 and 1.6-times higher As-extraction rates than the SDT and HIDS-only washing, respectively, under acidic conditions. The proposed approach with a binary blend of a biodegradable surfactant and chelator is a green solution for recycling As-contaminated excavated soils for geotechnical applications.

Tartaric acid soil-amendment increases phytoextraction potential through root to shoot transfer of lead in turnip

The phytoextraction potential of turnip and comparative effectiveness of three different organic ligands towards removal of lead (Pb) was investigated under field conditions. The 20 d old turnip seedlings were exposed to different Pb levels (0.0218, 2.42 and 4.83 mM Pb) spiked in the soil. After 10 d of Pb application, the soil was spiked with 2.4 mM concentration of different chelates viz. ethylenediaminetetraacetic acid (EDTA), citric acid (CA) and tartaric acid (TA). The 60 d old plants were harvested for growth analyses and determination of photosynthetic pigments, while Pb-concentration in different plant parts was determined from 60 and 90 d old plants. Yield attributes were recorded at the harvesting stage (HS, 90 d old plants). No suppression (rather a stimulation) in the root and shoot growth was evident upon Pb exposure whereas, a reduction in the chlorophyll content occurred at 4.83 mM Pb level. Soil amendment with TA improved chlorophyll contents irrespective of Pb levels while the effect of CA and EDTA was differential. A reduction in the root length while an increase in its diameter was recorded particularly at 4.83 mM Pb stress in 90 d old plants. The turnip retained maximum Pb-fraction in the roots at early growth stages, while EDTA application further increased its retention in root at 4.83 mM Pb regime. Nonetheless, only TA amendment promoted the transfer of Pb to shoot (∼30%) irrespective of Pb regimes. At the HS, application of both TA and EDTA caused substantial uptake of Pb in the root while the maximum shoot Pb-fraction was recorded again due to TA application, particularly at 4.83 mM Pb level. Above all, TA was identified as the most effective chelate that mobilized Pb from root to shoot leading to better growth possibly due to dilution effect, and thus enhanced phytoextraction efficiency in turnip.

Sustainable extraction of hazardous metals from crystal glass waste using biodegradable chelating agents

Extraction of hazardous metals from dumped crystal glass waste was investigated for site decontamination and resource recovery. Mechanically activated glass waste was leached with biodegradable chelating agents of ethylenediamine-N,N′-disuccinic acid (EDDS) and nitrilotriacetic acid (NTA), where the concentration and reaction time were determined by using Box–Wilson experimental design. Hazardous metals of lead (Pb), arsenic (As), antimony (Sb) and cadmium (Cd) with concentrations higher than regulatory limits were extracted wherein the extraction yield was found to vary Pb > Sb > As > Cd. Extraction was influenced more by type and concentration of chelator rather than by reaction time. A maximum of 64% of Pb could be extracted by EDDS while 42% using NTA. It is found that increase of chelator concentrations from 0.05 M to 1 M did not show improved metal extraction and the extraction improved with reaction time until 13 h. This study provides sustainable alternative for treating hazardous glass waste by mechanical activation followed by extraction using biodegradable chelator, instead of acid leaching.Graphical abstract

Determination of inert and labile copper on GEOTRACES samples using a novel solvent extraction method

Copper, in seawater, is predominantly bound by organic ligands of unknown composition. Complexation has been thermodynamically characterized using synthetic ligand competition experiments which assumes equilibrium among all chelators within the system. However, equilibration times are constrained by wall loss issues with the synthetic ligands. Here, a solvent extraction methodology, was utilized to avoid the wall-loss problems. Using an exceptionally high concentration of a strong copper chelator, oxine (8-hydroxyquinoline), at least six hours of equilibration time is required to reach steady state between the competing ligand and the labile copper in seawater. This is much longer than equilibration times used in previously published works. Our method was optimized by using samples from GEOTRACES expeditions in the North Pacific and North Atlantic Oceans. Surprisingly, 60–90% of the copper was not exchangeable with oxine under these conditions. We define this fraction as “inert”, and these data, which include profiles as deep as 1000 m in the North Pacific, suggest that this is a widespread feature. Our results suggest that there are two distinct pools of labile and inert copper, rather than an assemblage of similar complexes with incremental differences in stability constants. The results have important implications for the marine geochemistry of copper and its bioavailability. Complexation has been shown to limit copper bioavailability and influences scavenging and residence time. Moreover, a basic paradigm of copper speciation methodologies, that even strong Cu complexes are relatively labile, is likely incorrect.

Nat/89Zr][Zr(pypa)]: Thermodynamically Stable and Kinetically Inert Binary Nonadentate Complex for Radiopharmaceutical Applications.

H4pypa is a nonadentate nonmacrocyclic chelator, which previously demonstrated high affinity for scandium-44, lutetium-177, and indium-111. Herein, we report the highly stable binary [Zr(pypa)] complex; the nonradioactive complex was synthesized and characterized in detail using high-resolution electrospray-ionization mass spectroscopy (HR-ESI-MS) and various nuclear magnetic resonance spectroscopies (NMR), which revealed C2v symmetry of the complex. The geometry of [Zr(pypa)] was further detailed via X-ray crystallography and compared with the structure of [Fe(Hpypa)]. Despite a slow complexation rate with an association half-life of 31.4 h at pH 2 and room temperature, the [Zr(pypa)] complex is thermodynamically stable (log KML = 38.92, pZr = 39.4). Radiochemical studies demonstrated quantitative radiolabeling achieved at 10 μM chelator concentration within 2 h at 40 °C and pH = 7, antibody-compatible conditions. Of the utmost importance, [89Zr][Zr(pypa)] is highly kinetically inert upon challenge with excess EDTA and DFO ligands, superior to [89Zr][Zr(DFO)]+, and maintains inertness toward human serum.