Analysis of chromium and copper by cathodic stripping voltammetry with mixed ligands

Cathodic adsorptive stripping voltammetry is one of the most sensitive analytical methods for ultratrace analysis. The detection limit is usually lower than 10⁻⁹ mol/L. Most adsorptive stripping procedures have been focused on the one ligand/one analyte approach. In order to reduce analysis time and sample volume, the possibility of simultaneously determining several metals by cathodic stripping voltammetry using a mixture of ligands was explored, e.g., by Colombo and van den Berg (1997). Here, we describe a new procedure for quantifying chromium and copper using 2,2′-bipyridine and 8-hydroxyquinoline (oxine). The effect of various operational parameters such as buffer type, ligand concentration, potential and time collection were assessed and optimized. Possible interferences by trace metals and organic matter were also investigated. Applicability for fresh water is illustrated. Electronic Publication     

A straightforward synthesis in aqueous medium of enantiomerically enriched S(-)2,2′-dihydroxy-1,1′-binaphthyl

Chiral, atropisomeric 2,2'-dihydroxy-1,1'-binaphthyl has been extensively used to direct asymmetric processes. Its key role in asymmetric catalysis has spurred efforts to synthesize it in the optically pure form, but the reported synthetic routes have a significant environmental impact. In an aqueous peroxydase-cyclodextrin system the oxidative coupling of 2-naphthol took place very rapidly in almost quantitative yield and resulted in an enantiomeric excess. This one-pot synthesis do not require any organic solvents and oxidising metal cations.     

Investigation of the complexation of metal-ions by strong ligands in fresh and marine water

SCOPE: The detection and investigation of metal ions bound in strong complexes in natural waters is a difficult task, due to low concentration of the metal ions themselves, and also of the strong ligands, which, moreover, are often not of a well-defined composition. Here, a method is proposed for the investigation of the speciation of metal ions in natural waters. OBJECTIVE AND METHOD: It is based on the sorption of metal ions on strongly sorbing ion exchange resins, i.e. complexing resins. For this reason the method is called Resin Titration. It has been shown in previous investigations that the concentration of metal ion totally sorbed by a particular resin, and its reaction coefficient in the solution phase in the presence of the resin, can be determined from the sorption data using a simple relationship. Here, a data treatment (the Ruzic linearization method) is proposed for also determining the concentration of the ligands responsible for the complex in equilibrium with the resin. RESULTS: The method was applied to data obtained by Resin Titration of a freshwater and a seawater. Copper(II) and aluminium(III) were considered, using Chelex 100 as a titrant, due to its strong sorbing properties towards these metal ions. The results were: the total metal concentration in equilibrium with the resin, the side reaction coefficients, and the concentration of ligands. In all these cases the ligands forming very strong complexes were found to be at concentration lower than that of the metals. CONCLUSION: The Ruzic linearization method allows the determination of the concentration of the ligands forming very strong complexes in equilibrium with Chelex 100. The reaction coefficient was better determined by the calculation method previously proposed for RT. The ligands responsible for the strong complexes were found to be at low concentration, often lower than that of the metal ions considered. The metal in the original sample is partly bound to these ligands, since the complexes are very strong. Only a part of the metal is linked to weaker ligands, or free.     

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.     

金属浓度,半透膜孔径,水温及配位体对半透膜囊吸收铜的影响

在实验室条件下，研究了影响树脂－半透膜囊吸收铜的主要因素，重点探讨了水相铜含量，半透膜孔径，温度以及天然河水中的有机配位体对吸收的影响。结果表明，半透膜囊吸收量与水相游离铜浓度，水温及半透膜孔径的非整数次幂成正比，其中包括ＥＤＴＡ，河水富里酸，以及河水中的各种天然有机物在内的配位体均与铜生成不能被半透膜囊吸收的络合物，研究结果进一步证实了半透膜囊对水环境中游离态微量金属进行长期监测的可行性。     

Amelioration of free copper by hydrothermal vent microbes as a response to high copper concentrations

We examined the effect of increased copper concentrations (0–10 μM) on hydrothermal vent micro- organisms and the production of copper (Cu)-binding ligands as a response. Hydrothermal vent microbes originated from diffuse fluids at the Lilliput mussel field and the Irina II site in the Logatchev hydrothermal vent field, both on the Mid-Atlantic Ridge. Parallel studies were also conducted with amino acids supplemented to the incubations in order to verify whether dissolved amino acids, present in hydrothermal fluids, can buffer the bioavailable copper and reduce the active production of Cu-binding ligands. In all incubations, ligand concentrations increased with rising copper concentrations, but microbial cell numbers remained constant. This study shows that microbes were able to cope with as much as 10 μM dissolved copper by buffering the free copper concentration. The presence of amino acids had no significant influence on the active ligand production. Our results imply that mediation of chemical speciation by vent microbes may have an important impact on hydrothermal trace metal fluxes into the ocean.     

Organic ligand-induced dissolution kinetics of antimony trioxide

The influence of low-molecular-weight dissolved organic matter(LMWDOM) on the dissolution rate of Sb_2O_3 was investigated. Some representative LMWDOMs with carboxyl, hydroxyl,hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen, namely oxalic acid, citric acid, tartaric acid, EDTA, salicylic acid, phthalandione, glycine, thiolactic acid,xylitol, glucose and catechol. These LMWDOMs were dissolved in inert buffers at pH = 3.7, 6.6and 8.6 and added to powdered Sb_2O_3 in a stirred, thermostatted reactor(25°C). The addition of EDTA, tartaric acid, thiolactic acid, citric acid and oxalic acid solutions at pH 3.7 and catechol at pH 8.6 increased the rate of release of antimony. In the 10 mmol/L thiolactic acid solution, up to 97% by mass of the antimony was released after 120 min reaction. There was no effect on the dissolution of Sb_2O_3 for the other ligands. A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found. All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb_2O_3 was not determined by the stability of the dissolved complex, but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface. This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands, but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals.     

Preparation,characterization and toxic activity of oxovanadium(IV) mixed-ligand complexes

New oxovanadium(IV) mixed-ligand complexes of the general composition [VO(L)(A)], where KHL?=?potassium salt of salicylideneglycine, A¹?=?bis(benzylidene)ethylenediamine, A²?=?bis (acetophenone)ethylenediamine, A³?=?di(2-pyridyl)amine, A⁴?=?bis(benzylidene)-1,8-diaminonaphthalene, A⁵?=?thiophene-o-carboxaldene-aniline, A⁶?=?thiophene-o-carboxaldene-p-anisidine, have been synthesized by the interaction of these ligands with vanadyl sulphate. The mixed-ligand complexes have been characterized on the basis of elemental analysis, magnetic measurements, electronic and infrared spectra. An octahedral structure has tentatively been assigned to all of the mixed-ligand complexes. The mixed-ligand complexes show higher toxic activity against the Salmonella typhi, Escherichia coli and Serratia mercescen as compared to the ligands, vanadyl sulphate and control (dimethyl sulphoxide). The mixed-ligand complexes were also tested against a standard drug (tetracycline).     

Heavy-metal ion complexation by particulate matter in the leachate of solid waste: a multi-method approach

The metal ion binding characteristics of particulate matter obtained from column experiments on the anaerobic digestion of solid waste were studied using a titrimetric approach. The experimental set-up allowed us to study the dynamics of particle bound ligand concentrations during digestion processes typically found in landfills.We developed a continuous titration method by simultaneously using a Cd-sensitive and pH electrode and combining metal and acid/base titrations. This technique allows for a more precise determination of pK_a-log K_M pairs for each ligand than metal titrations alone. The results were compared with titration methods using differential pulse anodic stripping voltammetry (DPASV) and atomic absorption spectroscopy (AAS) with longer equilibration times in order to further characterize ligand properties such as reaction kinetics, the electrochemical lability of the respective complex during DPASV, the distinction between metal adsorption to particulate matter and metal complexation by soluble ligands adhered to particles, reversibility of the binding process by competition studies, and resistance against purging with nitrogen gas.The properties of seven major metal binding ligands were identified and assignments to the most likely functional groups were made. The most important ligand properties are for ligand A: pK_a ≈ 9.2, log K_cd ≈ 7.0 fast reaction kinetics (mercapto groups); ligand B: pK_a = 4.8, log K_Cd ≈ 6.0, slow reaction kinetics (chelates with 3 or 4 carboxylic groups); ligand C: pK_a ≈ 6.0, log K_Cd ≈ 13.0, irreversible metal binding at basic pH-values (uptake inside bacterial cells); ligand D: pK_a = 7.7, log K_Cd = 4.0, runs parallel to N content of particulate matter with digestion time (primary amines neighboring oxo groups); ligand E: pK_a ≈ 12.0, log K_Cd = 9.0, runs parallel to P content of particulate matter (phosphate); ligand F:pK_a > 9.0, log K_{Cdf = pKa + 0.4}, runs parallel to N content of particulate matter (primary amines neighboring SH groups); and ligand G: pK_a ≤ 4.8, log K_Pb ≈ 4.3, strong Pb²⁺ ligand, even at low pH-values.Metal ions were found to be irreversibly bound by ligand C at low heavy-metal concentratins, whereas at higher concentrations the binding is reversible and can be predicted using the mass of the digestion process (methanogenic phase). All other ligands have their concentration maximum in the transition phase between acetogenic and methanogenic phase.     

Hydroxyiminodisuccinic acid (HIDS): A novel biodegradable chelating ligand for the increase of iron bioavailability and arsenic phytoextraction

The influence of biodegradable chelating ligands on arsenic and iron uptake by hydroponically grown rice seedlings (Oryza sativa L.) was investigated. Even though the growth solution contained sufficient Fe, the growth of rice seedlings gradually decreased up to 76% with the increase of pH of the solution from 7 to 11. Iron forms insoluble ferric hydroxide complexes at neutral or alkaline pH in oxic condition. Chelating ligands produce soluble ‘Fe–ligand complex’ which assist Fe uptake in plants. The biodegradable chelating ligand hydroxyiminodisuccinic acid (HIDS) was more efficient then those of ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) in the increase of Fe uptake and growth of rice seedling. A total of 79 ± 20, 87 ± 6, 116 ± 15, and 63 ± 18 mg dry biomass of rice seedlings were produced with the addition of 0.5 mM of EDDS, EDTA, HIDS, and IDS in the nutrient solution, respectively. The Fe concentrations in rice tissues were 117 ± 15, 82 ± 8, 167 ± 25, and 118 ± 22 μmol g⁻¹ dry weights when 0.25 mM of EDDS, EDTA, HIDS, and IDS were added to the nutrient solution, respectively. Most of the Fe accumulated in rice tissues was stored in roots after the addition of chelating ligands in the solution. The results indicate that the HIDS would be a potential alternative to environmentally persistent EDTA for the increase of Fe uptake and plant growth. The HIDS also increased As uptake in rice root though its translocation from root to shoot was not augmented. This study reports HIDS for the first time as a promising chelating ligand for the enhancement of Fe bioavailability and As phytoextraction.