Effects of organic acid fractions extracted from Eucalyptus camaldulensis leaves on root elongation of maize (Zea mays) in the presence and absence of aluminium

Complexes of aluminium (Al) with organic ligands are believed to represent an important detoxification mechanism in acid soils. However, relatively little is known about the particular ligands produced by decomposing vegetation or about their effects on plant growth in the presence or absence of toxic Al. This paper reports an experiment on the effects of decomposition products of Eucalyptus camaldulensis leaves on the root elongation of maize (Zea mays) cv. DK687 in the presence or absence of Al. The static solution culture experiment used fulvic acid (FA) and humic acid (HA), extracted from E. camaldulensis leaves, at three nominal concentrations, viz. 40, 120 and 360 mg C L^-1, replicated 4 times in the presence and absence of 30 µM Al. In the absence of Al, root elongation was increased by 30% by HA at 40 mg C L^-1 and by 36% by FA at 120 mg C L^-1. In the presence of 30 µM Al, the effects of toxic Al on root elongation were negated by FA and HA at all concentrations. Aluminium was totally complexed in all treatments except FA at 40 mg C L^-1 in which treatment only 2.7 µM Al was present in the monomeric form. The E. camaldulensis FA and HA at concentrations of 40 and 120 mg C L^-1, either in the presence or absence of Al, stimulated maize root elongation. Aluminium was strongly complexed by the E. camaldulensis FA and HA. The present results, in which FA and HA alleviated Al toxicity limitations on root elongation of maize, are relevant to the protection afforded to plant growth in acid soils amended with organic materials. They highlight the need to focus more on the role of FA and HA.     

Effect of organic Cr(III) complexes on chromium speciation

Abstract

Chromium speciation in the presence of organic chromium(III) complexes was investigated using solid-phase extraction. The adsorptions of Cr(VI) and Cr(III) on alumina and pumice powder were studied. Maximum sorption of Cr(VI) was obtained by alumina (90.22%), while Cr(III) was highly adsorbed onto pumice powder (86.65%). This result shows that pumice may be a new and promising adsorbent for Cr(III). The experimental equilibrium data for Cr(VI) adsorption onto alumina and Cr(III) sorption onto pumice were analysed using Langmuir and Freundlich isotherms. The separation and adsorption of Cr(VI), Cr(III) and five organic chromium(III) complexes onto pumice and alumina at different pH values were evaluated. Ethylenediaminetetraacetate (EDTA), oxalate, citrate, glycine, alanine and 8-hydroxyqinoline were used as ligands. Sorption of alanine and ethylenediaminetetraacetate complexes was higher onto alumina than pumice at pH>3. The enhancement of adsorption of chromium(III) complexes onto pumice was achieved by surface modification of pumice using a surfactant, namely hexadecyltrimethylammoniumbromür (HDTMA). The presence of surfactant enhanced the adsorption of Cr(III) citrate, oxalate, glycine and 8-hydroxyquinoline complexes onto pumice. However, the adsorption of EDTA and alanine complexes decreased, with ratio of 13.40% and 4.00% respectively. Here we demonstrate that chromium speciation methods depending on adsorption onto various adsorbents including alumina may lead erroneous results. Analytical measurements were performed by flame AAS, data were obtained by standard addition method.     

Novel chelating agents as manganese and zinc fertilisers: characterisation,theoretical speciation and stability in solution

Abstract

Mineral, complex and chelated micronutrient fertilisers are widely used in agriculture. However, there have been few studies on manganese and zinc fertilisers. In fact, specific chelating agents to provide these micronutrients to plants have not been found, in contrast to iron. This work considers the interactions of novel and traditional ligands in micronutrient mixtures used in hydroponics and fertigation. Theoretical speciation studies comparing the stability in solution have been carried out to simulate the possible interactions that can affect Fe, Mn and Zn in aqueous formulations containing these micronutrients. Unknown stability constants of ligands with Zn and Mn have been determined. Also, theoretical speciation investigations in hydroponic conditions have been carried out. It has been found that the new chelating agents, IDHA and EDDS, and the poorly studied o,p-EDDHA, can be good alternatives to the traditional sources such as EDTA, HEEDTA and DTPA principally for Zn fertilisers. The Mn and Zn chelates with o,p-EDDHA and complexes with lignosulfonate and gluconate have also shown high stability in a hydroponic nutrient solution, maintaining more than 80% Mn in solution until pH 10. The presence of o,o-EDDHA/Fe³⁺ and o,p-EDDHA/Fe³⁺ enhances the stability of Zn in solution in the mixed fertilisers. More studies with substrates are necessary to confirm these results and to extend them to other agronomic conditions.     

Removing radionuclides from wound fluids using chemical speciation and chelation lavage

Abstract

The relative efficacy of a range of chelating agents for dissolving plutonium(IV) hydroxide precipitated in wounds is assessed by computing the chemical speciation prevailing in the wound fluid and wound lavage solution. The most promising ligand for mobilisation is DTPA when used under mildly acid (approx. pH 6.4) conditions. If the Pu(IV) oxide has been formed, none of the ligands are effective.     

Copper sorption by chitosan in the presence of citrate ions: influence of metal speciation on sorption mechanism and uptake capacities

The presence of organic ligands in a solution containing metal ions modifies metal speciation, which in turn changes the sorption mechanism, optimum pH range and maximum sorption capacity. The present work investigates the sorption of copper by chitosan in the presence of citrate at different metal/ligand ratios. Copper uptake in acidic solution takes place through electrostatic attraction between the protonated amine groups of chitosan and anionic copper-citrate complexes (mainly Cu(OH)L2- but also a small fraction of CuL-). Sorption was negligible below pH 3 due to competition from dissociated anionic ligand and counter ions brought about by dissociation of the acid used for pH control. Actually, copper sorption begins to be significant when the fraction of anionic copper-complexes exceeds that of anionic copper-free ligand. So sorption capacity strongly increases up to pH 4.5-5.5. Above pH 5.5, the progressive decrease of amine protonation leads to a linear decrease in sorption capacity. An excess of ligand leads to an increase in the fraction of free dissociated (anionic) ligand that may compete for electrostatic attraction on protonated amine groups and therefore leads to a decrease in sorption capacities.     

Re-evaluating the effects of organic ligands on copper toxicity to barley root elongation in culture solution

Abstract

In the presence of weak ligands, both free ion activity and organic complexes of Cu should b considered when predicting Cu toxicity in aquatic and soil-plant systems. However, there is littl information about the quantitative contribution of Cu that is organically complexed to Cu toxicity. In thi study, a bioassay using barley root elongation in culture solution was used to investigate the effects o organic ligands with different conditional stability constants on Cu toxicity and the quantitativ contribution of the organically complexed Cu to the Cu toxicity. The results indicated that a significan decrease (p<0.05) in Cu toxicity, assessed by barley root elongation, was observed in response to th addition of organic ligands. The decrease differed, to some extent, with different organic ligands o disodium ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), oxalate and malate at low and constant free Cu²⁺ activity. Addition of EDTA or NTA resulted in strong reduction of Cu toxicity while modest reduction of Cu toxicity was observed for the addition of malate as the relatively wea ligand. Furthermore, the results of the present study revealed that the CuNTA^? and CuEDTA^2? complexes were not toxic, while the Cu–malate complexes were mildly toxic to barley root elongation More importantly, it was found that the toxicity of Cu–malate complexes were nearly 0.5-fold less than that of free Cu²⁺ ions.     

Metal speciation in xylem and phloem exudates

Summary Two computer programs based on simultaneous chemical equilibria were compared for calculation of chemical species in xylem exudates. The first program, CHELATE, was developed to calculate the chemical species in xylem exudates while GEOCHEM was developed to calculate the speciation of natural aquatic systems. The output of the two programs should be similar since they are based on similar calculations. Data input to the programs consisted of concentration data for Ca, Cu, Fe, Mg, Mn, Zn, NH₄, PO₄, pH and 28 organic ligands reported for xylem exudates from soybean (Glycine max (L.) Merr.) and tomato (Lycopersicon esculentum Mill.) plants grown in nutrient solution¹⁷. The organic ligands included amino acids and low molecular weight organic acids (e.g., citric and malic). With the exception of Fe, there were large differences between CHELATE and GEOCHEM in the calculated speciation of nearly all metals in the xylem exudates. In general, there was better agreement between the programs for the speciation of alkaline earth metals than for transition metals. Discrepancies between the two programs were attributed to differences in 1) species considered and 2) stability constants. GEOCHEM considered a greater number of possible complexes. In addition, stability constants for some complexes differed by as much as 10 fold between the two programs. When the data base for GEOCHEM and CHELATE were the same, the output from CHELATE and GEOCHEM was almost identical. Thus, computations performed by the two programs are equally valid, but it is essential that the data base used in chemical models be verified before interpreting the output. Average concentration data for Al, Au, Ca, Cu, Fe, K, La, Mg, Mn, Na, Rb, Zn, Cl, MoO₄, PO₄, SO₄, HVO₄, pH and 18 organic ligands in phloem exudates from Yucca (Yucca flaccida Haw.) were complied from available literature and analyzed by GEOCHEM. Amino acids were the predominant organic ligand analyzed. Calculations revealed that alkali metals existed almost totally as the free ionic species (≥99%) whereas alkaline earth metals were transported as complexes with organic acids (oxalic, malic, and asparagine). Aluminum and Fe were present as hydroxyl species while <1% of micronutrients were transported as the free ion. Major micronutrient species were Cu-glutamine, Mn-asparagine and Zn-alanine. Information on calculated species present in phloem exudates could be useful to guide studies for isolation of metal-ligand complexes in phloem exudates.     

A multivariate analysis of health risk assessment,phytoremediation potential,and biochemical attributes of Spinacia oleracea exposed to cadmium in the presence of organic amendments under hydroponic conditions

Abstract

Cadmium (Cd) phytoremediation potential and its accumulation in edible and nonedible plant tissues is the function of various biochemical processes taking place inside plants. This study assessed the impact of organic ligands on Cd phyto uptake and different biophysiochemical processes of Spinacia oleracea L., and associated health hazards. Plants were exposed to Cd alone and chelated with citric acid (CA) and ethylenediaminetetraacetic acid (EDTA). Results revealed that the effect of Cd on lipid peroxidation, H₂O₂ production and pigment contents varied greatly with its applied level and the type of organic ligand. Moreover, the effect was more prominent in root tissues than leaf tissues and for high concentrations of Cd and organic ligands. Cadmium accumulation increased by 90 and 74% in roots and leaves, respectively, with increasing Cd levels (25–100?µM). Cadmium exposure at high levels caused lipid peroxidation in roots only. Application of both CA and EDTA slightly diminished Cd toxicity with respect to pigment contents, lipid peroxidation and hydrogen peroxide (H₂O₂) contents. Hazard quotient (HQ) of Cd was <1.00 for all the treatments. Under nonlinear effect of treatments, multivariate analysis can be an effective tool to trace overall effects/trends.     

Cobalt toxicity in anaerobic granular sludge: influence of chemical speciation

The influence of cobalt speciation on the toxicity of cobalt to methylotrophic methanogenesis in anaerobic granular sludge was investigated. The cobalt speciation was studied with three different media that contained varying concentrations of complexing ligands [carbonates, phosphates and ethylenediaminetetraacetic acid (EDTA)]. Three fractions (nominal added, dissolved and free) of cobalt were determined in the liquid media and were correlated with data from batch toxicity experiments. The average concentration of cobalt that was required for 50% inhibition of methanogenic activity (IC₅₀) for free Co²⁺ in the three sets of measurements was 13 μmol/L with a standard deviation of 22% and a similarity of 72% between the data obtained in the three different media for the range of cobalt concentrations investigated. The standard deviation of the IC₅₀ for the other two fractions was much higher, i.e. 85 and 144% for the added cobalt and dissolved cobalt, respectively, and the similarity was almost 0% for both fractions. Complexation (and precipitation) with EDTA, phosphates and carbonates was shown to decrease the toxicity of cobalt on methylotrophic methanogenesis. The free cobalt concentration is proposed to be the key parameter to correlate with cobalt toxicity. Thus, the toxicity of cobalt to granular sludge can be estimated based on the equilibrium-free cobalt concentration.     

Selenium speciation analysis in the cerebrospinal fluid of patients with Parkinson’s disease

BackgroundThe aim of the study was to investigate if speciation analysis by liquid chromatography coupled to mass spectrometry could be used to detect organic and inorganic binding forms of selenium in the cerebrospinal fluid (CSF) of patients with Parkinson’s disease (PD) and age-matched control subjects (AMC).MethodsPD patients and control subjects were enrolled from three different neurological departments. CSF samples were collected according to standardized biomarker protocols and subjected to inductively coupled plasma mass spectrometry (ICP-MS) for total selenium determination and ion exchange chromatography (IEC) hyphenated to ICP-MS for selenium speciation analysis.Results75 PD patients and 68 age-matched controls were enrolled for speciation analysis. 8 different species could be detected, but only selenoprotein P (SELENOP), human serum albumin-bound Se (Se-HSA), selenomethionine (Se-Met) and an unidentified Se-compound (U2) presented with more than 50% values above the limit of quantification, without showing significant differences between both groups (p > 0.05). The Se-HSA / Se-Met ratio yielded a significant difference between PD and AMC (p = 0.045). The inorganic species Se-IV and Se-VI were only detectable in a minor part of PD and AMC samples. A highly significant correlation between total selenium levels and SELENOP (PD p < 0.0001; AMC p < 0.0001) and Se-HSA (PD p < 0.0001; AMC p < 0.0001) could be demonstrated, respectively.ConclusionsSpeciation analysis yielded new insight into selenium homeostasis in PD but cannot be used to establish a diagnostic biomarker. The small number of detectable values for Se-IV and Se-VI suggests an inferior role of these potentially neurotoxic binding forms in PD pathology in contrast to other neurodegenerative disorders.     

Potential of Sonchus Arvensis for the Phytoremediation of Lead-Contaminated Soil

Sonchus arvensis is one of the pioneer plant species that were found in the abandoned Bo Ngam Pb mine in Thailand. S. arvensis was collected from three sites. The highest Pb shoot concentration was 9317 mg kg^?1 and the highest translocation factor (TF) and bioaccumulation factor (BF) values were 2.5 and 6.0, respectively. To investigate Pb uptake capacity of S. arvensis, a hydroponic experiment was performed for 15 d. S. arvensis exposed to 5 mg L^?1 Pb solution had the highest Pb shoot accumulation (849 mg kg^?1). In a pot study, S. arvensis was grown in Pb mine soils amended with organic and inorganic fertilizers for 2 mo. The addition of organic fertilizer to the soil increased plant dry biomass sharply. All treatments with ethylene-diamine-tetra-acetic acid (EDTA) had Pb accumulation in shoots greater than 1000 mg kg^?1 and the highest Pb shoot accumulation was found in S. arvensis grown in soil amended with organic fertilizer and EDTA (1397 mg kg^?1). In a field trial study, S. arvensis was grown at three sites in the mine area for 6 mo. S. arvensis could tolerate a total Pb of 100,000 mg kg^?1 in the soil and accumulated Pb in the shoots up to 3664 mg kg^?1 with high TF (2.19) and BF (2.38) values. These results suggest that S. arvensis is a good candidate for Pb phytoremediation.     

Time evolution of Pb(II) speciation in Pampa soil fractions

Abstract

Soil pollution by heavy metals, particularly lead, is an important environmental concern; the bioavailability of such pollutants is strongly dependent on their chemical form. Here, the speciation of Pb(II) in soil fractions as a function of time shortly after its incorporation is studied, using a selective sequential extraction method. The sample came from an Argentinean Pampas region and was extensively characterised, including Rietveld analysis of the silt+clay fraction XRD pattern to find the major mineral components. Experiments were run twice, once in the winter and once in the summer. The results show different speciation time profiles in both cases, showing faster changes in winter due to the higher water content. The summer experiment corresponds to an earlier stage in the speciation profile evolution compared with winter. The soluble/exchangeable fraction decreases with time in summer but shows a lower and constant value in the winter. A high proportion is found to be adsorbed onto the stable (aluminosilicates+quartz) mineral fraction. The results strongly suggest that, even at a short time following soil pollution with Pb, a high proportion is adsorbed onto the mineral fraction, with only a low fraction being bioavailable. The most stable (mineral incorporated) form is observed to increase with time. Soil water content appears to be more important than temperature in determining the differences between the two.     

Effect of sample pretreatment upon the metal speciation in sediments by a sequential extraction procedure

Abstract

Sample pretreatment, such as drying, is sometimes necessary for the speciation analysis of trace metals in sediments. However, this pretreatment may exert some effects upon the speciation distribution. In this study, the heavy metals (Cu, Pb, Cr, Cd, Zn and Ni) in reservoir surface sediments were fractionated to water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), organic matter and sulfide bound (B3) by a three-stage sequential extraction procedure. The effect of different drying methods (oven-drying at 85^oC, air-drying at 20°C and freeze-drying) on metal speciation distribution was investigated. Compared to the fresh wet sample, none of the drying methods completely preserve the initial chemical speciation distribution of the elements. The B1 fraction was particularly sensitive to sample pretreatment methods. Among the elements, zinc was especially perturbed by air-drying, care must be exercised because air-drying was commonly used in sediment pretreatment.     

Chemical speciation of aluminium in beers

ABSTRACT

Details of analyses of a range of lagers for aluminium and for silica are presented. These permit an estimation of the total levels of aluminium as beer is diluted by saliva and intestinal fluids. These data are combined with databases of formation constants and solubility products and the MINEIR speciation program to calculate the chemical speciation of aluminium from beer through to excretion. Bioavailable species are assumed to be [Al citrate]⁰ and/or [Al phosphate]⁰ but other than a noticeable presence in the small intestine—from which uptake is limited there is not a significant species concentration. With normal kidney action any small traces entering the blood are rapidly cleared.     

Aluminium in tea: SEC-ICP-MS speciation studies of infusions and simulated gastrointestinal digests

Abstract

The speciation of aluminium in tea infusions and in vitro gastrointestinal digests of tea infusions has been investigated using size exclusion chromatography coupled to inductively coupled plasma mass spectrometry (SEC-ICP-MS). At pH 2.5, following simulated gastric treatment, Al from tea eluted at a similar retention volume to that obtained for an aqueous Al standard. At pH 5.5, an aqueous Al standard was eluted from an SEC column in Tris buffer (Al recovery ≈ 100%) only in the presence of a complexing agent (NaF), and at a retention volume corresponding to a molecular mass greater than that expected for an ionic species. Aluminium associated with a tea infusion eluted in two fractions: a higher molecular weight fraction corresponding to Al strongly bound to ligands in the tea, and a lower molecular weight fraction probably comprised of labile Al eluting as Al-F complexes. Simulated gastrointestinal digestion produced three Al-bearing fractions, of which the two at higher molecular mass represented ligand-bound Al. The molarity of the Tris buffer strongly influenced the retention volume of the Al fractions, particularly for the ligand-bound Al. After simulated gastrointestinal digestion, the soluble labile fraction (15% of the Al from the tea infusion) was considered to be potentially available for absorption. The actual proportion of the fraction that might be absorbed would depend upon a number of physiological and nutritional factors.     

Sequential extraction and speciation of Ba,Cu, Ni,Pb and Zn in soil contaminated with automotive industry waste

Abstract

Sequential extraction or fractionation of heavy metals in the solid phase and their speciation in soil solution are important tools for assessing changes resulting from land use and/or pollution. The distribution of the various forms of Ba, Cu, Ni, Pb and Zn was evaluated in soil samples taken from a polluted area, and the speciation of cations and anions in a soil solution contaminated with automotive industry waste. We evaluated the sequential extraction and speciation of Ba, Cu, Ni, Pb and Zn in a Leptosol associated with a Cambisol and contaminated with automotive industry waste. Soil samples were collected at 0-0.2 m (a mix of soil and waste); 0.2-0.4 m (waste only), and 0.4-0.6 m (soil only) both in the polluted area and in two contiguous unpolluted areas: a sugarcane plantation and a forest fragment. Total concentrations of metals in the polluted area were above limits for intervention established by European Community regulations. Cu was mostly distributed in the residual and in the oxide-bonded fractions, except for the waste-only sample, in which the carbonate-bonded fraction was significant. Zn was concentrated in the residual and carbonate-bonded fractions, while Ba, Ni and Pb predominated in the residual fraction of the contaminated samples. Metals in the soil solution were predominantly in the hydroxyl forms, except for Ba, which was mostly in the ionic form (Ba²⁺).     

The influence of pH and chloride on the retention of cadmium,lead, mercury,and zinc by soils

The extent of contamination of soils by toxic heavy metals not only depends on the rate of loading of the metal but also on the nature of the adsorbing surfaces, the degree of alkalinity or acidity of the soil and the presence of aqueous complexant ligands. This work reports on the role of pH on the retention of Cd, Hg, Pb and Zn by two soils and on the influence of the chloride, Cl‐, ion on the chemical speciation and retention of the four metals. Batch adsorption experiments were conducted from pH 3 to 7 in the presence of either 0.1 M LiCl or LiClO₄. The results of the study showed that high concentrations of Cl^‐ ions can greatly decrease the retention of Hg and have an increasingly lesser effect on Cd, Pb and Zn retention. The effect of the Cl^‐ons was directly related to the metal‐Cl formation constants. The results of computer modeling of Cd and Hg retention by goethite and humic acid fractions indicated the relative importance of aqueous vs. surface complexation on metal retention. For organic surfaces, which do not form ternary surface complexes, the presence of aqueous complexant ligands should always decrease the adsorption of the metal. For mineral surfaces, which do form ternary surface complexes, there may be increased or decreased metal retention depending on the formation constant of the aqueous metal‐ligand species, the intrinsic complexation constants for the various binary and ternary complexes of the metal and the concentration of the complexant ligand. Thus for Hg, which forms very strong aqueous species with Cl^‐ ions, reduced adsorption on goethite was predicted in the presence of 0.1 M LiCl, while enhanced adsorption was predicted for Cd and Pb. The results suggest caution in the disposal of Cl‐containing wastes onto metal‐contaminated soils. The deleterious effects of Cl^‐ ion addition would be greatest for soils with relatively high organic matter contents and low contents of hydrous ferric oxides.     

Population differentiation without speciation

Population differentiation is often viewed as an important step towards speciation, and part of the rationale for conserving variation at the intraspecific level is that the potential to generate more biological diversity should be retained. Yet, speciation is not an inevitable consequence of population divergence. This paper reviews recent work on the Trinidadian guppy, Poecilia reticulata, a species that is renowned for its capacity for population differentiation. Guppy populations evolve rapidly, within 10¹ to 10² generations, as a response to changes in selection exerted by predators. The rates of evolution involved can be up to seven orders of magnitude greater than those seen in the fossil record. Sexual selection, particuarly female choice, appears to reinforce the divergence that natural selection has generated. Perplexingly, however, there is no reproductive isolation (either prezygotic or postzygotic) between populations, even those that have been separated for at least 10⁶ generations. Sexual conflict may be the key to explaining this absence of speciation. Male reproductive behaviour, particularly the high incidence of sneaky mating, may be instrumental in producing sufficient gene flow to prevent reproductive isolation. Sneaky mating has the potential to undermine female choice, and is known to be an important means of sperm transfer in wild populations. Sexual dimorphism, also a result of sexual conflict in guppies, may inhibit speciation in another way. Morphological differences between the sexes, that have arisen for reproductive reasons, mean that males and females are pre-adapted for different foraging niches. This, in turn, reduces the opportunity for the development of feeding polymorphisms, a mechanism that seems to have been important in the sympatric speciation of other fish species.     

Quantitative speciation of heavy metals in soil and crops of agricultural fields of Islamabad,Pakistan

Abstract

Two root crops: carrot (Daucus carota) and spring onion (Allium fistulosum) and soil samples were selected from the agricultural fields located near Islamabad, Pakistan to determine their elemental content. Field soil speciation of the two crops was also carried out to analyse the correlation of the elements in field crop and soil. Concentrations of selected elements were evaluated in the leaf, stem, root and flowering part of the crops using flame atomic absorption spectrophotometry. The results showed that elements are mostly concentrated in soil rather than crop parts following the sequence Zn>Cu>Pb>Ni>Cr>Cd. Furthermore, soil speciation showed that Ni and Cr are more prevalent in the Fe–Mn oxide fraction, Zn and Cd as the carbonate bound fraction and Cu is found in the organic bound form. However, concentrations of Pb are similar across the carbonate, Fe–Mn oxide and organic bound fractions. The highest average concentration of Zn is found as the carbonate bound fraction (2.09 ± 0.005 mg kg^?1) and Cu as the organic bound (1.51 ± 0.029 mg kg^?1) in soil samples taken from the agricultural field of Daucus carota.     

Bioavailability and speciation—the case of inorganic compounds

Abstract

The stability constants of binary complexes of 2,4-dichlorophenoxyacetic acid (2,4-D), (4-chloro-2-methylphenoxy)acetic acid (2,4-MCPA) and (4-chloro-2-methylphenoxy) propionic acid (2,4-MCPP) with Hg(II), Pb(II) have been calculated at 298 K and at ionic strength μ = 0.1 (NaNO₃). Potentiometric measurements display two hydroxide complexes for Hg(II): HgH_?1A and HgH_?2A₂ whereas for Pb(II) we observe the formation of three species PbH_?1A, PbH_?1A₂ and PbH_?2A₂. With regard to the successive complexes, no other system represents this type of complexes under our experimental conditions. The order of capacity of complexation compared to metal for the three ligands is Hg(II)4Pb(II). Finally, the study in solution has been completed by a quantum examination of the structures of the complex of Hg(II) by the AM1 method.