Formation and stability of binary complexes of divalent ecotoxic ions (Ni, Cu, Zn, Cd, Pb) with biodegradable aminopolycarboxylate chelants (dl-2-(2-carboxymethyl)nitrilotriacetic acid, GLDA, and 3-hydroxy-2,2′- iminodisuccinic acid, HIDS) in aqueous solutions

The protonation and complex formation equilibria of two biodegradable aminopolycarboxylate chelants {dl-2-(2-carboxymethyl)nitrilotriacetic acid (GLDA) and 3-hydroxy-2,2′-iminodisuccinic acid (HIDS)} with Ni 2+, Cu2+, Zn2+, Cd2+ and Pb 2+ ions were investigated using the potentiometric method at a constant ionic strength of I = 0.10 mol·dm-3 (KCl) in aqueous solutions at 25 ± 0.1 C. The stability constants of the proton-chelant and metal-chelant species for each metal ion were determined, and the concentration distributions of various complex species in solution were evaluated for each ion. The stability constants (log10 K ML) of the complexes containing Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ ions followed the identical order of log10 K CuL > log10 K NiL > log10 K PbL > log10 K ZnL > log10 K CdL for either GLDA (13.03 > 12.74 > 11.60 > 11.52 > 10.31) or HIDS (12.63 > 11.30 > 10.21 > 9.76 > 7.58). In each case, the constants obtained for metal-GLDA complexes were larger than the corresponding constants for metal-HIDS complexes. The conditional stability constants (log10 $$K-{\text{ML}}^{\u27}$$) of the metal-chelant complexes containing GLDA and HIDS were calculated in terms of pH, and compared with the stability constants for EDTA and other biodegradable chelants. © 2012 Springer Science+Business Media New York

Remediation of toxic metal contaminated soil by washing with biodegradable aminopolycarboxylate chelants

Ex situ soil washing with synthetic extractants such as, aminopolycarboxylate chelants (APCs) is a viable treatment alternative for metal-contaminated site remediation. EDTA and its homologs are widely used among the APCs in the ex situ soil washing processes. These APCs are merely biodegradable and highly persistent in the aquatic environments leading to the post-use toxic effects. Therefore, an increasing interest is focused on the development and use of the eco-friendly APCs having better biodegradability and less environmental toxicity. The paper deals with the results from the lab-scale washing treatments of a real sample of metal-contaminated soil for the removal of the ecotoxic metal ions (Cd, Cu, Ni, Pb, and Zn) using five biodegradable APCs, namely [S,S]-ethylenediaminedisuccinic acid, imminodisuccinic acid, methylglycinediacetic acid, DL-2-(2-carboxymethyl) nitrilotriacetic acid (GLDA), and 3-hydroxy-2,2\u27-iminodisuccinic acid. The performance of those biodegradable APCs was evaluated for their interaction with the soil mineral constituents in terms of the solution pH and metal-chelant stability constants, and compared with that of EDTA. Speciation calculations were performed to identify the optimal conditions for the washing process in terms of the metal-chelant interactions as well as to understand the selectivity in the separation ability of the biodegradable chelants towards the metal ions. A linear relationship between the metal extraction capacity of the individual chelants towards each of the metal ions from the soil matrix and metal-chelant conditional stability constants for a solution pH greater than 6 was observed. Additional considerations were derived from the behavior of the major potentially interfering cations (Al, Ca, Fe, Mg, and Mn), and it was hypothesized that use of an excess of chelant may minimize the possible competition effects during the single-step washing treatments. Sequential extraction procedure was used to determine the metal distribution in the soil before and after the extractive decontamination using biodegradable APCs, and the capability of the APCs in removing the metal ions even from the theoretically immobilized fraction of the contaminated soil was observed. GLDA appeared to possess the greatest potential to decontaminate the soil through ex situ washing treatment compared to the other biodegradable chelants used in the study. © 2012 Elsevier Ltd

Stability constants of Fe(III) and Cr(III) complexes with dl-2-(2-carboxymethyl)nitrilotriacetic acid (GLDA) and 3-hydroxy-2,2\u27- iminodisuccinic acid (HIDS) in aqueous solution

The complex formation equilibria of Cr3+ and Fe3+ ions in aqueous solution with two biodegradable aminopolycarboxylate chelants (dl-2-(2-carboxymethyl)nitrilotriacetic acid (GLDA) and 3-hydroxy-2,2\u27- iminodisuccinic acid (HIDS)) were investigated. The potentiometric data obtained at the constant ionic strengths (I) of (0.1 and 1.0) mol·dm-3 KCl and at (25 ± 0.1) °C was processed with the aid of the computer program HYPERQUAD 2008. The formation constants of the proton-chelant and metal-chelant (log KML) species (M = Fe3+ or Cr 3+; L = GLDA or HIDS) were determined, and the concentration distributions of complex species in solution were evaluated for both metal ions. In various pH conditions, the interaction between the chelants (L = GLDA or HIDS) and the metal ions (M = Fe3+ or Cr3+) leads to the formation of different complexes formulated as MH2L+, MHL, ML-, M(OH)L2-, and M(OH)2L3-. The log KML values at I = 0.1 mol·dm-3 KCl (T = (25 ± 0.1) °C) were 15.27 (log KFe-GLDA), 14.96 (log K Fe-HIDS), 13.77 (log KCr-GLDA), 12.67 (log K Cr-HIDS), and at I = 1.0 mol·dm-3 KCl (T = (25 ± 0.1) °C) were 14.79 (log KFe-GLDA), 14.34 (log K Fe-HIDS), 12.90 (log KCr-GLDA), 12.09 (log K Cr-HIDS). The conditional stability constants (log K\u27ML) of the ML complexes were calculated in terms of pH in the range of 2 to 12 and compared with the same for EDTA and other biodegradable chelants (NTA and EDDS). © 2012 American Chemical Society

Binding of proton and iron to lignite humic acid size-fractions in aqueous matrix

金沢大学理工研究域物質化学系The bioavailability of trivalent iron (Fe3+) to plants can be enhanced using fertilizer solutions containing humic acids (HA) as manifested from the increased crop yield at an iron stress conditions. The lignite-derived HA (HAlignite) facilitates higher diffusion of Fe3+ between the soil layers as attributable to more number of reactive sites in the assemblage compared to those from other origins. In the current work, the proton-binding of HAlignite size-fractions (5–10, 10–30, 30–100, and >100 kDa), as segmented based on the molecular weight distribution, and their complexation with Fe3+ have been studied at varying pH ranging from low to high. The protonation or formation of Fe3+-complexes exhibited a comparable pattern despite the differences in the conformational distribution of HAlignite size-fractions. The protonation behavior specified that the behavior of HAlignite size-fractions has similarity with that of a dibasic acid. The results are interpreted using reactive structural units (RSU) concept to show that the carboxyl and phenolic-hydroxyl groups in the HAlignite size-fractions simultaneously available as the Fe3+-binding sites. The stability constants for larger MW fractions of HAlignite (>100 kDa) was the lowest, as attributed to the increased aggregation rate in an aqueous matrix. The trend in conditional stability constants of HAlignite-size fractions and other Fe-chelators point to a better Fe-binding capability of HAlignite (30–100 kDa) size-fraction than the biodegradable alternatives (GLDA, HIDS, EDDS, IDSA, or NTA), while the Fe-interaction was stronger with classical synthetic chelators (EDTA, DTPA, or EDDHA). © 2018 Elsevier B.V.Embargo Period 12 month

Laboratory culture experiments to study the effect of lignite humic acid fractions on iron solubility and iron uptake rates in phytoplankton

The major fractions of dissolved iron in seawater exist as a complex with organic ligands. A high bioavailability of iron bound to humic acid (HA) compared to the other model ligands, such as desferrioxamine B or ferrichrome, has been reported, which implies the importance of HA to control the geochemical behavior and the transfer of Fe to marine phytoplankton, particularly in estuarine and coastal waters. In the current work, the effect of different HA fractions (>100, 100–30, 30–10, 10–5, and 5–3 kDa), which were extracted from lignite, on the comparative solubility of iron in seawater and the corresponding influence on iron uptake and growth rate of the phytoplankton Prymnesium parvum (Haptophyta) was studied using laboratory cultures. The lower-molecular-weight (MW) HA fractions, such as 30–10, 10–5, and 5–3 kDa, remained soluble in the simulated seawater medium for a longer time span compared to the higher MW fractions. The lower MW fractions facilitated higher iron solubility and assisted in achieving a better phytoplankton growth rate. However, a reciprocal impact on phytoplankton growth rates was observed when the HA concentration increased to a higher range (0.18 to 18 mg-C L−1). The highest intracellular Fe uptake in phytoplankton occurred with 30–10 kDa HA in seawater, and the extracellular dissolved Fe concentrations were higher for smaller-sized HA fractions. In summary, our study showed that the controlled addition of lower MW fractions of HA (up to 30–10 kDa) in estuarine waters could ensure the accelerated uptake of Fe in phytoplankton as well as a better growth rate. © 2016 Springer Science+Business Media DordrechtEmbargo Period 12 month