Cd-EDTA Complex Research Articles

Dechelation of Cd-EDTA complex and recovery of EDTA from simulated soil-washing solution with sodium sulfide

Washing water containing poorly degradable heavy metal-EDTA complexes is produced by ethylenediaminetetraacetic acid (EDTA) washing of heavy metal-contaminated soil. A series of batch experiments were performed to explore the dechelation of heavy metal-EDTA complexes and the recovery of EDTA from simulated soil-washing solution using sulfide precipitation with Na2S. The results showed that the effect of Na2S dosage on the dechelation of Cd-EDTA solution was greater than that of other factors (reaction temperature, time, and pH) and excess EDTA suppressed cadmium removal. Additionally, the Cd removal efficiency reached 99.99 ± 0.001%, and the residual amount of Cd-EDTA was below the detection limit of ion chromatography (IC) measurements under the following optimal conditions: an initial Cd-EDTA solution pH of 6, a sodium sulfide-to-Cd-EDTA ratio of 2:1, a reaction temperature of 25 °C, and a contact time of 20 min. Furthermore, the results of analysis using inductively coupled plasma optical emission spectroscopy (ICP-OES), Fourier transform infrared (FT-IR) spectroscopy, and ion chromatography (IC) confirmed that the dechelation process could be completed in less than 20 min and that EDTA was completely recovered as trisodium EDTA (HNa3EDTA). The mechanism for the dechelation of Cd-EDTA and recovery of EDTA using sulfide precipitation with Na2S was also proposed. The recovered EDTA with acidification had the same ability to extract heavy metals from soil with fresh EDTA. This study may facilitate the recycling of soil-washing wastewater and reduce the cost of extracting heavy metals from soil using EDTA.

Comparative effect of organic amendments on physio-biochemical traits of young and old bean leaves grown under cadmium stress: a multivariate analysis.

The current study investigated the influence of organic amendments on cadmium (Cd) uptake and its effects on biochemical attributes of young and old leaves of bean. Bean seedlings were exposed to two levels of Cd (25 and 100μM) in the presence and absence of different levels of ethylenediaminetetraacetic acid (EDTA) and citric acid (CA). An increase in Cd concentration in growth medium significantly enhanced Cd accumulation in bean roots and shoot. Cadmium stress increased the production of H2O2 which resulted in lipid peroxidation and decreased chlorophyll contents. The presence of organic amendments significantly affected Cd accumulation and toxicity to bean plants. Application of EDTA alleviated Cd toxicity in terms of chlorophyll contents, H2O2 contents, and lipid peroxidation possibly by chelating toxic Cd ions, and as such forming Cd-EDTA complexes. The presence of CA decreased Cd toxicity by decreasing its uptake. The biochemical responses (H2O2 contents, lipid peroxidation, and chlorophyll contents) of bean plants were more severely affected by Cd treatments in old leaves compared to young leaves. This study shows that the effect of CA and EDTA on biochemical behavior of Cd varies greatly with applied levels of Cd and amendments as well as the age of leaves. Based on the results, it is proposed that the presence of organic amendments can greatly affect biogeochemical behavior of Cd in the soil-plant system (ecosystem).

Complexation of DTPA and EDTA with Cd2+: stability constants and thermodynamic parameters at the soil-water interface.

Two alkaline soils collected from the surface horizon (0-15cm) of two agricultural fields Lakshmikantapur (LKP; 22° 06' 03″ N and 88° 18' 19″ E) and Diamond Harbour (DHB; 22° 11' N and 88° 14' E) of West Bengal, India were studied to observe the stability of cadmium (Cd) chelate complexes with diethylenetriaminepentaacetatic acid (DTPA) and ethylenediaminetetraacetic acid (EDTA), removing organic matter (OM). The objective of the present study is "determination of the stability constants and the thermodynamic parameters of Cd-DTPA and Cd-EDTA complexes at different pH and temperatures at the soil-water interface". Complex formation of soil Cd with DTPA and EDTA at the soil-water interface was studied under different ligand-to-metal ratios, pHs and temperatures. Apparent conditional stability constants (log k´) were calculated from the concentrations of Cd chelates and free Cd2+, estimated by solid phase extraction with an ion exchanger. Standard Gibbs energy (ΔG°), standard enthalpy (ΔH°) and standard entropy (ΔS°) of formation were calculated at three different temperatures. The higher stability constants of Cd-DTPA than Cd-EDTA indicated longer persistence of Cd-DTPA at the soil solution interface than Cd-EDTA complex. Increase of ΔG°, ΔH° and ΔS° with progress of temperature revealed that Cd-complex formation was facilitated by temperature. Highly negative ΔG° and positive ΔH° for Cd-complex formation indicated the reaction spontaneous and exothermic. In general, both ligands complexed high percentages of cadmium signalling their role in enhancing remobilization of Cd present in soil and preventing exchange of contaminated Cd from external source with soil mineral matrix; these phenomena may greatly reduce hazard for environment and human health. The result of this study support that DTPA increases solubility and more persistence of Cd in acidic soils within the range of temperature and mole fraction (MF=moles of Cd2+/sum of the moles of Cd2+ and chelating agent) than that of EDTA due to higher capability of complex formation with Cd2+. Therefore, DTPA enhanced Cd toxicity in acid soils and groundwater. Complex formation in the presence of DTPA at acidic pH decreases with temperature and increases with pH. The higher per cent of Cd complexed in the presence of DTPA revealed that DTPA is a stronger chelating agent than EDTA at acidic pHs. Whereas, the capability of complex formation by EDTA is lower at lower pH but higher at higher pH.

Quick, easy, cheap, effective, rugged and safe strategy for quantifying cadmium polluted rice

ABSTRACTCadmium (Cd) pollution is an environmental concern in China. Animals and humans are at risk for Cd poisoning through the consumption of Cd-contaminated rice. A fast and convenient on-site Cd detection tool is required. In this study, we developed a Quick, Easy, Cheap, Effective, Rugged and Safe method to detect Cd in rice. This immunochromatographic method is based on a Cd monoclonal antibody, which recognizes Cd-EDTA complexes. Rice Cd was extracted with 0.1 M HCl under vigorous shaking, transferred to a dispersive solid phase extraction column, and eluted with perchloric acid. Cd recovery was ∼50%. The detection range of our developed method was 0.02–0.8 mg Cd/kg rice with LOD 0.02 mg/kg. The results obtained by immunochromatography which was applied to 71 samples were compared with those obtained via inductively coupled plasma mass spectrometry; the correlation coefficient between these two methods was 0.95. Therefore, our developed method was fast and simple and can be used for on-site Cd detection.

Contribution of Cd-EDTA complexes to cadmium uptake by maize: a modelling approach

Background and aims Chelant-enhanced phytoextraction has given variable and often unexplained experimental results. This work was carried out to better understand the mechanisms of Cd plant uptake in the presence of EDTA and to evaluate the contributions of Cd-EDTA complexes to the uptake.

High sensitive gold-nanoparticle based lateral flow Immunodevice for Cd2+ detection in drinking waters

In this work for first time a lateral flow immunosensor device (LFID) for Cd2+ determination in drinking and tap waters using the Cd–EDTA–BSA–AuNP conjugate as signal producer tool is introduced. The principle of working is based on competitive reaction between the Cd–EDTA–BSA–AuNP conjugate deposited on the conjugation pad strip and the Cd–EDTA complex formed in the analysis sample for the same binding sites of the 2A81G5 monoclonal antibody, specific to Cd–EDTA but not Cd2+ free, which is immobilized onto the test line. The device has a large response range within 0.4–2000ppb, being the linear response between 0.4 and 10ppb. The quantification and detection limits of 0.4 and 0.1ppb, respectively, represent the lowest ones reported so far for paper based metal sensors. The obtained detection limit is 50 times lower than the maximum contamination level required for drinking water. Here we also show a new option for increasing the sensibility in the LFDs with competitive format, through the decreasing in concentrations of the Cd–EDTA–BSA–AuNP conjugate deposited in the conjugation strip and the mAbs deposited in the test and control zones until to reach optimized concentrations. It is an important result take into account that the increase in sensibility is one of the challenges in the field of LFD sensors, where are focused many of the ongoing researches. In addition, a specificity study of the device for several metal interferences, where potential metal interferences are masked with the use of the EDTA and OVA optimized concentrations, is presented too.

All-Integrated and Highly Sensitive Paper Based Device with Sample Treatment Platform for Cd2+ Immunodetection in Drinking/Tap Waters

Nowadays, the development of systems, devices, or methods that integrate several process steps into one multifunctional step for clinical, environmental, or industrial purposes constitutes a challenge for many ongoing research projects. Here, we present a new integrated paper based cadmium (Cd(2+)) immunosensing system in lateral flow format, which integrates the sample treatment process with the analyte detection process. The principle of Cd(2+) detection is based on competitive reaction between the cadmium-ethylenediaminetetraacetic acid-bovine serum albumin-gold nanoparticles (Cd-EDTA-BSA-AuNP) conjugate deposited on the conjugation pad strip and the Cd-EDTA complex formed in the analysis sample for the same binding sites of the 2A81G5 monoclonal antibody (mAb), specific to Cd-EDTA but not Cd(2+) free, which is immobilized onto the test line. This platform operates without any sample pretreatment step for Cd(2+) detection thanks to an extra conjugation pad that ensures Cd(2+) complexation with EDTA and interference masking through ovalbumin (OVA). The detection and quantification limits found for the device were 0.1 and 0.4 ppb, respectively, these being the lowest limits reported up to now for metal sensors based on paper. The accuracy of the device was evaluated by addition of known quantities of Cd(2+) to different drinking water samples and subsequent Cd(2+) content analysis. Sample recoveries ranged from 95 to 105% and the coefficient of variation for the intermediate precision assay was less than 10%. In addition, the results obtained here were compared with those obtained with the well-established inductively coupled plasma emission spectroscopy (ICPES) and the analysis of certificate standard samples.

Degradation of the EDTA and EDTA complexes with metals by immobilized cells of Chelativorans oligotrophicus LPM-4 bacteria

Enzymatic oxidative degradation of EDTA and EDTA complexes with metals has been investigated using immobilized cells of Chelativorans oligotrophicus LPM-4. A polarographic method, which makes it possible to register oxygen consumption by cells, has been used. For the first time, it has been indicated that the Cd-EDTA and Ni-EDTA complexes undergo degradation by the bacteria under study.

Preparation of hapten-specific monoclonal antibody for cadmium and its ELISA application to aqueous samples

High-affinity and specific monoclonal antibodies against cadmium-ethylene diamine tetraacetic acid (EDTA) complex have been produced using the hybridoma technique. A hapten was synthesized and characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and UV-Vis. Competitive enzyme-linked immunosorbent assay (ELISA) for quantitative detection of cadmium in aqueous sample was developed. The monoclonal antibody with high level of binding affinity for Cd-IEDTA-BSA and high specificity for soluble Cd-EDTA complex showed less than 0.99% cross-reactivity with other 11 metals. The limit of detection was 0.10 μg·L−1, and the effective linear range was 10−1–103 μg·L−1. The intra- and inter-assay coefficient variations were 1.5%–6.3% and 3.2%–7.4%, respectively. The spike recovery in different water samples were between 98.5% and 110.3%. The detection limit of this assay was well below the allowable concentration of cadmium (3 μg·L−1), and the working range was wider than that of other methods which showed the range of 2.19–86.38 and 0–103 μg·L−1. The competitive ELISA established in this paper was sensitive and accurate in the screening of cadmium in aqueous samples. The results will lay a solid foundation for construction of an immunoassay kit for cadmium.

Role of Bound Zn(II) in the CadC Cd(II)/Pb(II)/Zn(II)-responsive Repressor

The Staphylococcus aureus plasmid pI258 cadCA operon encodes a P-type ATPase, CadA, that confers resistance to Cd(II)/Pb(II)/Zn(II). Expression is regulated by CadC, a homodimeric repressor that dissociates from the cad operator/promoter upon binding of Cd(II), Pb(II), or Zn(II). CadC is a member of the ArsR/SmtB family of metalloregulatory proteins. The crystal structure of CadC shows two types of metal binding sites, termed Site 1 and Site 2, and the homodimer has two of each. Site 1 is the physiological inducer binding site. The two Site 2 metal binding sites are formed at the dimerization interface. Site 2 is not regulatory in CadC but is regulatory in the homologue SmtB. Here the role of each site was investigated by mutagenesis. Both sites bind either Cd(II) or Zn(II). However, Site 1 has higher affinity for Cd(II) over Zn(II), and Site 2 prefers Zn(II) over Cd(II). Site 2 is not required for either derepression or dimerization. The crystal structure of the wild type with bound Zn(II) and of a mutant lacking Site 2 was compared with the SmtB structure with and without bound Zn(II). We propose that an arginine residue allows for Zn(II) regulation in SmtB and, conversely, a glycine results in a lack of regulation by Zn(II) in CadC. We propose that a glycine residue was ancestral whether the repressor binds Zn(II) at a Site 2 like CadC or has no Site 2 like the paralogous ArsR and implies that acquisition of regulatory ability in SmtB was a more recent evolutionary event.

Simplified method for determining cadmium concentrations in rice foliage and soil by using a biosensor kit with immunochromatography

AbstractBACKGROUND: The behavior of cadmium in ecosystems needs to be monitored because of the human toxicity of this heavy metal. The need recently arose for a simple and quick on‐site test for trace levels of Cd in food and environmental samples. In response, an immunochromatographic assay kit for detecting Cd was manufactured by Kansai Electric Power Co. of Japan. This kit uses the antigen–antibody complex reaction between the Cd–EDTA complex and an anti‐Cd–EDTA antibody and shows the results in terms of the degree of color developed on a test paper. We previously reported the successful use of this kit to determine Cd concentrations in brown rice. Here, we applied the kit to the determination of Cd concentrations in rice foliage and soil.RESULTS: Cadmium in rice foliage was not extracted successfully by the method used for brown rice. However, it was successfully extracted by 0.1 mol L−1 HCl solution at a rice foliage:HCl ratio of 1:20, and coexisting metals were removed sufficiently by the column treatment. The Cd concentrations determined by immunochromatographic assay were well correlated with the values obtained by acid decomposition and inductively coupled plasma mass spectrometry. The 0.1 mol L−1 HCl‐extractable Cd concentration in soil was also determined successfully with the kit.CONCLUSION: Approximate Cd concentrations in rice plants and 0.1 mol L−1 HCl‐extractable Cd concentrations in soil can be monitored easily and quickly by this method at locations where facilities for acid digestion and precision analysis are not available. Copyright © 2009 Society of Chemical Industry

Complex-assisted one-step synthesis of ion-exchangeable titanate nanotubes decorated with CdS nanoparticles

Trititanate nanotubes were prepared from anatase TiO 2 in 10 M Na 2S solution kept at 130 °C for 2 weeks. On the basis of this reaction, we devised a novel synthesis method which allows the preparation of titanate nanotubes decorated with CdS nanoparticles in one step. The key feature of the suggested method is controlling the rate of CdS formation by introducing Cd 2+ ions as a Cd–EDTA complex into the synthesis mixture. The nanotubes obtained are several hundred nm long, tend to aggregate into rod-like structures and are fully covered by CdS nanoparticles with an average diameter of ∼5.3 nm.

Trace metal determination by dc resistance changes of microstructured thin gold film electrodes

The deposition of adatoms onto the surface of a thin metal film can increase its lateral dc resistance. The magnitude of the increase is related to the surface coverage. We have utilized this phenomenon for the determination of heavy metal concentrations in aqueous solution. Using thin gold films as working electrodes in a three electrode arrangement, we deposited cadmium, lead, nickel, thallium and zinc ions as well as Cd-EDTA complexes and measured the corresponding resistance changes. Different species could be distinguished from each other. For cadmium ions a linear relationship between the induced resistance change and the cadmium concentration has been achieved over a concentration range between 4 ng/g and 1 μg/g.

Complexometric determination of cadmium using 2-Mercaptoethanol as masking reagent

A complexometric method for the determination of cadmium(II) in presence of other metal ions is described based on the selective masking ability of 2-mercaptoethanol towards cadmium(II). Cadmium and other ions in a given sample solution are initially complexed with excess of EDTA and the surplus EDTA is titrated with lead nitrate solution at pH 5.0–6.0 (hexamethylentetramine), using xylenol orange as indicator. A known excess of 2-mercaptoethanol solution (10% alcoholic) is then added, the mixture is shaken well and the released EDTA from the Cd-EDTA complex is titrated against standard lead nitrate solution. The interferences of various ions are studied and the method is applied to the determination of cadmium in its complexes. Reproducible and accurate results are obtained for 3.5–25mg of Cd with relative errors ≤ 0.65% and standard deviations ≤ 0.06 mg.

Indirect complexometric determination of cadmium(II) using 1,10-phenanthroline as selective masking agent

An indirect complexometric method is described for the determination of cadmium(II), 1,10-phenanthroline being used as masking agent. Cadmium(II) in a given sample solution is initially complexed with an excess of EDTA and the surplus EDTA is titrated with lead nitrate solution at pH 5.0–6.0 (hexamine), using xylenol orange as indicator. An excess of 1,10-phenanthroline is then added and the EDTA released from the Cd-EDTA complex is titrated with standard lead nitrate solution. Results are obtained for 1.5–57 mg of Cd with relative errors ≤0.90% and standard deviations ≤0.06 mg. Cu(II), Co(II), Hg(II), Ni(II), Zn(II), Pd(II), Tl(III), Au(III) and Sn(IV) interfere, but can be easily masked. The method is applied for the determination of cadmium in synthetic alloy solutions.

Formation Mechanism of Monodisperse CdS Particles from Concentrated Solutions of Cd–EDTA Complexes

The formation mechanism of monodisperse spherical CdS particles in a condensed homogeneous solution of Cd–EDTA complexes in the presence of thioacetamide (TAA), ammonium acetate, ammonia, and gelatin was studied. The monodisperse particles were formed through a consecutive process with an almost instantaneous nucleation and succeeding gradual growth without renucleation. The Cd–EDTA and TAA worked only as reservoirs of Cd2+and S2−ions, but the rate-determining step of particle growth was found to be the dissociation process of the Cd–EDTA complexes and not of the TAA. Ammonia played a decisive role as a complexing agent at high concentrations of Cd(NH3)2+n, which could promptly release free Cd2+ions, in promoting nucleation as well as growth even under a low supersaturation, and thus achieved excellent monodispersity by lowering the supersaturation below the critical level during their growth. The important role of CH3COONH4–NH3as a powerful pH buffer for maintaining the activity of both NH3and TAA was also proved. Moreover, size control of the final product was achieved in a range from 0.038 to 0.51 μm.

Substitution complexometric determination of cadmium in the presence of zinc in homogeneous water—organic solvent medium

A method for substitution complexometric determination of cadmium is based on the decomposition of the Cd—EDTA complex by the combined action of ethylxanthate and zinc. The reaction is performed in a slightly acid homogeneous water—organic solvent medium in which the cadmium ethylxanthate complex is stable and soluble.

The uptake and distribution of cadmium in tomato plants as affected by ethylenediaminetetraacetic acid and 2,4-dinitrophenol

The uptake and distribution of cadmium in tomato plants ( Lycopersicon esculentum, Mill, cv. Tiny Tim) were examined with and without the presence of ethylenediaminetetraacetic acid (EDTA) as chelating agent and 2,4-dinitrophenol (DNP) as metabolic inhibitor. Eight-week-old intact and derooted tomato seedlings were used in hydroculture experiments with cadmium applied as 115Cd(NO 3) 2 in a range of concentrations. Measurements of the 115Cd content of roots, stems and leaves were carried out by γ-ray spectroscopy. The data showed that applications of both EDTA and DNP resulted in reduced total Cd accumulation in the plants, but relatively enhanced Cd transport into the above-ground plant parts. The Cd mobility in the transport channels in the shoots was increased by EDTA in both intact and derooted plants. Application of DNP leads to increased relative Cd import to leaves in derooted plants, but a reduced import into leaves of intact plants. These results suggest that Cd-complexes are formed in root cells before root-to-shoot transport. Furthermore, initial Cd uptake may be associated with adsorption on the negative charges of the cell walls of the root system. The high Cd mobility in shoots, in experiments with intact plants and Cd-EDTA application, indicates the possibility of simultaneous uptake of Cd and EDTA, possibly as a Cd-EDTA complex.

The influence of some complexing agents (EDTA and citrate) on the uptake of cadmium in perfused rainbow trout gills

The cadmium transfer through and the retention of metal in perfused gills from rainbow trout ( Salmo gairdneri) has been studied in the presence of two Cd-complexing agents, ethylenediaminetetraacetic acid (EDTA) and citrate. The transfer and retention of Cd in the presence of EDTA was almost a function of the ambient free Cd 2+ activity. The transfer of the free Cd ion was about 1000 times higher than of the Cd-EDTA complex. The Cd-EDTA complex was to some extent retained in perfused tissue. The transfer of Cd in the presence of citrate was markedly greater than expected on the basis of the free Cd 2+ activity. The tissue retention of Cd was not affected by the presence of citrate. It is concluded that Cd uptake in fish gills in the presence of complexing agents is not simply a function of complexed versus free metal. The uptake is also profoundly dependent on the type of complexing agent present.

Effects of chelating agents on oral uptake and renal deposition and excretion of cadmium.

The gastrointestinal absorption, transport, tissue deposition and excretion of cadmium was studied in adult male mice given a single oral LD50 dose of 109Cd-labeled CdCl2 alone or in combination with nitrilotriacetic acid (NTA), sodium tripolyphosphate (STPP) or ethylenediaminetetraacetic acid (EDTA). Blood, intestinal mucosa, liver and kidneys were analyzed for 109Cd at different times after exposure and the influence of the chelating agents on Cd binding to metallothionein and other tissue ligands was also studied. Acute toxicity was noted. Complex formation between Cd and EDTA was studied in solutions containing Cd:EDTA at 1:04 and 1:4 molar ratios. Adult male mice were exposed orally or by direct infusion into the stomach to either of the two solutions (containing an LD50 dose of Cd). Body retention and tissue deposition of Cd was recorded after 4 (direct infusion) or 21 days (oral exposure), and the mortality in different exposure groups observed. Adult male were also exposed to a low oral dose of 109Cd-labeled cadmium (0.5 mg/kg), followed by 18 months continuous administration of NTA, (500 ppm) STPP (500 ppm) or EDTA (50 ppm) in the drinking water or the chelating agent in combination with Cd (50 ppm), Cd alone (50 ppm) or deionized water. Whole-body retention of 109Cd, tissue deposition of 109Cd and total Cd and development of proteinuria were observed. When cadmium was given with an excess of EDTA, all Cd ions were bound in a 1:1 Cd-EDTA complex. Decreased acute toxicity was observed which was related to increased body elimination of cadmium. The Cd passes though the body still bound to EDTA and is excreted via the kidneys in this form. Similar results were found in mice exposed to Cd + NTA, while gavage of CD + STPP led to an initially decreased systemic uptake of Cd and thereafter to a prolongation of the biological half-time and thus a comparatively higher body retention of the metal. Cd may form a 2:1 complex with EDTA in the presence of excess cadmium. An increased retention and toxicity of cadmium was seen after direct infusion of this solution, while gavage resulted in a decreased toxicity. The effect of different chelating agents on acute cadmium toxicity and metabolism seemed to be due to changes in the stability of the administered chelate complexes, due to variation in pH and to the availability of metal binding ligands such as metallothionein in vivo. NTA, STPP and EDTA had no effect on the metabolism or toxicity of cadmium after long-term low dose oral exposure.