Dissolution of aluminum and iron phosphate by humic acids

Abstract

An investigation was conducted to study the effect of humic (HA) and fulvic acid (FA) on the dissolution of aluminum phosphate (AlPO₄) and iron phosphate (FePO₄), to analyze the dissolution products, and assess their availability to plants. The rate of dissolution was determined by shaking 10 mg of Al‐ or FePO₄ with 0 to 800 mg L^‐1 of HA or FA solutions at pH 7.0 for 0 to 192 hours. The phosphorus (P) concentration was measured in the extracts by spectrophotometry, whereas the nature of P‐humic acid complexes was determined by ³¹P NMR analysis. Availability of dissolution products was studied by growing corn plants in aerated hydroponic solutions receiving treatments of 50 mg Al‐ or FePO₄ and 0 to 800 mg L^‐1 of HA or FA at pH 5.0. The results indicated that the amount of P released by HA or FA increased with time. Humic acid was more effective than FA in dissolving the metal phosphates. The ³¹P NMR analysis showed that the dissolution products contained free orthophosphates and minor amounts of P‐humic acid complexes. This confirms the role of HA as a powerful chelator of Al and Fe, liberating in this way the orthophosphate anions. Corn plants grown in hydroponics, with AlPO₄ or FePO₄ as the source of P, exhibited better growth performance when HA or FA are present.     

Complexation of mercury(II) ions with humic acids in tundra soils

The interaction mechanisms of mercury(II) ions with preparations of humic acids (HAs) isolated from organic horizons of surface-gleyed soils (Haplic Stagnosol (Gelic, Siltic)) of shrub tundra and hydromorphic peat gley soils (Histic Cryosol (Reductaquic, Siltic)) of moss-lichen tundra have been studied. The particular features of the interactions between the mercury(II) ions and the HAs are related to the molecular structure of the HAs, the mercury concentration range, and the environmental parameters. The fixation of mercury(II) ions into stable coordination compounds is most efficient in the pH range of 2.5–3.5. At the element concentrations below 0.50 μmol/dm³, the main complexing sites of HAs are their peripheral aminoacid functional groups. Pyrocatechol, salicylate, and phenolic groups from the nuclear moiety of molecules interact in the concentration range of 0.0005–0.50 mmol/dm³; the physical sorption of mercury hydroxo complexes by the surface of HAs is the main process occurring in the system.     

Cosorption of phenanthrene and mercury(II) from aqueous solution by soybean stalk-based biochar

Soybean [Glycine max (L.) Merr.] stalk-based biochar was prepared using oxygen-limited pyrolysis. We evaluated phenanthrene (PHE) and Hg(II) sorption, from single and binary component solutions, onto prepared biochar. We found that the prepared biochar efficiently removed PHE and Hg(II) from aqueous solutions. The isotherms for PHE and Hg(II) sorption could be described using linear and Tóth models, respectively, both with high regression coefficients (R(2) > 0.995). When PHE and Hg(II) coexisted in an aqueous solution, we observed direct competitive sorption, each one suppressing another. Our results provide insight into the recycling of agricultural residues, and also a new application for removal of polycyclic aromatic hydrocarbons and heavy metals from contaminated water utilizing biochar from agricultural residue.     

Copper(II) binding by free and kaolinite-sorbed humic substances

Humic preparations isolated from different sources—soils (a soddy-podzolic soil and a typical chernozem), high-moor peat, and brown coal—have been used. To analyze the binding of copper ions by humic substances (HSs), the preparations were obtained in two forms: solutions and humic-clay complexes (HSs irreversibly sorbed on kaolinite). With this approach, the binding of copper(II) ions by HSs has been studied in different systems: (1) Cu(II)-HSs irreversibly sorbed on kaolinite, (2) Cu(II)-dissolved HSs, and (3) Cu(II)-dissolved HSs-HSs irreversibly sorbed on kaolinite. In the systems containing both dissolved HSs and humic-clay complexes, HSs of similar structure isolated from the same source were used. The quantitative estimation of the copper binding was based on the constant of sorption (K) for HSs in humic-kaolinite complexes and the stability constant (β) of complexes for free (dissolved) substances. Both parameters were expressed in similar units: L/kg. The values of logK = 3.31—3.33 are independent of the quantity and quality of the HSs in the sorption complexes but reliably exceed the K value for pure kaolinite (2.92). The value of β is not affected by the presence of insoluble HSs together with their soluble forms, but it depends on the source of HSs. The value of logβ varies in the range from 5.62 to 6.93, which significantly exceeds K and indicates a significantly higher affinity of dissolved HSs for copper ions than that of irreversibly sorbed HSs. The revealed regularities have shown that the content of HSs in the soil solution can significantly affect the mobility of a heavy metal bound to the soil organic matter.     

Aluminum and iron(III) species in the soil solution including organic complexes with citrate and humic substances

The solubility of Al and Fe in soil is of relevance for their toxicity and availability, respectively, to plant roots. Humic substances as the main part of stable soil organic matter and citrate which is often excreted by P deficient plants are strong complexants of Al and Fe(III). Therefore, equations were developed to calculate the Al and Fe(III) species distribution in the soil solution in the presence of humic substances and citrate as organic ligands. Calculations in the pH range 4.0–7.0 showed that at higher pH humic-Al complexes were the most important species whereas AlOH-citrate^? dominated between pH 4.0 and 5.4. Free monomeric Al and AlSO₄⁺ were of minor relevance. Iron(III) species calculations showed that humic-Fe complexes were the main species in the pH range 4.0–7.0. But if mugineic acid, a Fe complexing phytosiderophore released into the rhizosphere by graminaceous plant species, was present in the soil solution (10^?6 M), Fe-mugineic acid complexes accounted for most of the Fe in solution. Fe-citrate^? was relevant at lower pH but contributed little to Fe(III) species at pH > 6.0. The results demonstrate the strong importance of the considered organic ligands for Fe and Al in the soil solution.     

The relative efficiency of ionic iron(III) and iron(II) utilization by the rice plant

Uptake of iron by rice plants was equally rapid when supplied as ionic iron(II) or iron(III) at pH 3 and 4. Iron(III) uptake was reduced at pH 5 and uptake of iron when supplied as FeEDTA was relatively low at all three pH levels.

At pH 4 in the presence of plant roots, reduction of iron(III) to iron(II) occurred as indicated by Fe²⁺ BPDS formation. BPDS in a 3:1 ratio to iron(III) suppressed iron uptake by about 70%. The reduction was observed to be located in the endodermis of young roots and exodermis of older roots.

A capacity to oxidize iron(II) at the root surface was also observed under local anaerobic and relatively high pH conditions.

The significance of these two counteracting processes in affecting the oxidation state of iron at the root surface is discussed.     

Complexation of iron (III) to humic substances of a humic podzol at pH 2.5 - 6.4 - quantification of the organically complexed iron by pyrophosphate extraction

Bonding of Fe(III)-ions to humic substances of a humic podzol are reported with regard to pH (range 2.5 - 6.4). A separation technique is used involving a pyrophosphate extraction, whereby dissolved, precipitated, and organically bound iron can be separated. The necessity of iron speciation results from the fact that the amount of Fe bound to organic matter is overestimated if conventional methods are used. The estimation of formation constants for iron actually bound to organic matter leads to a corrected maximum value of log K'_f(org) = 1.64, whereas for the total eliminated Fe this maximum value is 2 units higher (log K'_f= 3.70).     

Properties of and heavy metal complexation by aqueous humic extracts

Aqueous extracts of terrestrial and underwater soils were prepared by Soxhlet extractions at temperatures between 100 and 37°C (under reduced pressure). From the law of mass action, stability constants were derived for the complexation of Cd, Cu, and Pb by these extracts. The activity of the heavy metals was determined polarographically, whereas the concentration of acid functional groups was used for ligand activity. Visible spectra, electrical conductivity, organic matter contents, and complexation constants depended on extraction temperature as well as on soil properties. In most cases, complex stability increased with increasing pH of the polarographic medium, but sometimes maximum stability was found around pH 7.     

Humus and humic acids in chernozems of the southeastern Transbaikal region (Chita Oblast)

Humic acids (HAs) in the noncalcareous chernozems developed from the colluvium of argillites and chlorite schist are characterized by a predominance of the first, relatively mobile fraction (HA-1) and a lower content of the second (HA-2) fraction. Modern nondestructive physicochemical methods for studying the chemical structure of HA macromolecules have shown that the Has in the virgin soils have approximately equal portions of aromatic and aliphatic groups. In the plowed soils, the portion of aromatic carbon increases under the impact of the intensive agricultural use of these soils and their susceptibility to wind erosion.     

Isomerization of trans-astaxanthin induced by copper(II) ion in ethanol

Carotenoids are unstable and susceptible to disruption by environmental factors such as heat, light, and solvents. However, there is little information on the effect of metal ions on stability of carotenoids, especially those essential elements in human nutrition. Astaxanthin is one of the few carotenoids containing four oxygen donors. Usually, these oxygen donors can coordinate with heavy metal ions such as Cu(II) and Fe(III). In the present study, the interaction of trans-astaxanthin with Cu(II) was examined. It was found that Cu(II) markedly induces the conversion of trans-astaxanthin to its cis forms, which mainly consist of 9-cis-astaxanthin and 13-cis-astaxanthin as suggested by UV-visible spectra and HPLC measurements. Increasing either incubation time of Cu(II) and trans-astaxanthin in ethanol or the Cu(II)/astaxanthin ratio results in an increased percentage of cis isomers derived from trans-astaxanthin. All these results provide important information on the effects of dietary factors on the bioavailability and bioactivity of trans-astaxanthin.     

On the components of soil humic acids (Part iv) on the absorption spectra of the components of B-type humic acid

Introduction

Concerning the A-type humic acid found in different kinds of soil the writers fractionated each of its components and measured its lightabsorbing power and compared the characteristics of those components.     

Removal of chromium (VI) as chromium diphenyl carbazide (CDC) complex from aqueous solution by activated carbon

Adsorption of Cr (VI) as CDC-complex from aqueous solution by activated C has been investigated. Factors like pH and presence of Cr (III) which affect the adsorption of CDC-complex were studied. The increase in particle size and surface area of activated C does not enhance the removal of CDC-complex. For different concentrations of Cr, the optimum quantity of Diphenyl Carbazide has been determined. The reduced Cr e.g. Cr (III) decreases the CDC-complex removal. The Langmuir and Freundlich isotherms constant as calculated are γm=1.8932 and b=0.2305 and n=0.036, log K=0.0266, respectively.     

On the components of soil humic acids (part 8) the oxidative decomposition by alkaline potassium permanganate and nitric acid

As for the reactions by oxidizing agents of humic acids and for the products obtained by the said reactions, a number of investigations (1) have been made with regard to the study of the chemical structure of humic acids and with the use of the products of decomposition. The authors (2) have observed that A-or B-types of soil humic acids could be separated into three or four fundamental composing fractions by using Al²O³ column.     

Speciation of phytate ion in aqueous solution. Sequestering ability toward mercury(II) cation in NaClaq at different ionic strengths

As a contribution to understanding the speciation of mercury in the environment and to the study of the sequestering ability of phytate (Phy) toward heavy metal and organometal cations, this paper describes the results of an investigation (at t = 25 degrees C by potentiometry, ISE-H+ glass electrode) of its interactions with mercury(II) cation in NaCl aqueous solutions at different ionic strengths (I = 0.15 and 1.0 mol L(-1)), in the pH range 2.5 < or = pH < or = 9.5 and considering metal-to-ligand ratios of 1:1 < or = Hg/Phy < or = 4:1. The formation of 11 HgiHjPhy(12-2i-j)(- species with i = 1 and 0 < or = j < or = 7 and i = 2 and 0 < or = j < or = 2 was observed. Their complex formation constant values proved to be fairly dependent on ionic strength. The speciation of phytic acid and mercury(II) is also dependent on the metal-to-ligand ratio; the dependence of the stability of phytate-mercury(II) species on the phytate protonation step was modeled, and an empirical predictive relationship was proposed. From the results obtained, phytate has very good sequestering ability toward Hg2+, even in the presence of considerable excesses of chloride ion, that is, another ligand strongly interacting with mercury; this supports future studies both on the use of plants that naturally synthesize it for phytoremediation purposes and on its direct application in remediation techniques.     

Selective digestion of the peptide and polysaccharide components of synthetic humic acids by the humivorous larva of Pachnoda ephippiata (Coleoptera: Scarabaeidae)

In order to identify the potential nutrient and energy sources of humivorous beetle larvae, we carried out feeding trials with soil supplemented with specifically ¹⁴C-labeled model humic acids synthesized by peroxidase-initiated radical polymerization, using the cetoniid beetle Pachnoda ephippiata (Coleoptera: Scarabaeidae) as a model organism. Ingestion of soil by the larvae significantly increased the mineralization of humic acids labeled in their peptide (HA-*peptide) or polysaccharide components (HA-*peptidoglycan and HA-*chitin), whereas the mineralization of humic acids labeled in the aromatic components (HA-*catechol) did not increase significantly. Mineralization was accompanied by a reduction of residual radiolabel in the acid-soluble fraction and an increase in the humic acid and humin fractions of the fecal pellets. During the gut passage, the residual label in peptide or polysaccharide components was transformed into acid-soluble products, especially in the alkaline midgut. High-performance gel-permeation chromatography demonstrated that the changes in solubility were accompanied by large changes in the molecular weight of the residual material. The amount of radiolabel derived from the peptide and polysaccharide components recovered from the larval body and hemolymph was significantly higher than that derived from the aromatic component, which supports the hypothesis that humivorous beetle larvae selectively digest the peptide and polysaccharide components of humic substances, whereas the aromatic components of humic substances are not an important source of nutrients and energy. This is also the first experimental evidence that also chitin and peptidoglycan, the major structural polymers in fungal and bacterial biomass, can be protected from microbial degradation in soil by a copolymerization with phenols and might contribute substantially to the refractory nitrogen pool in soil organic matter.     

Effects of phthalic and salicylic acids on Cu(II) adsorption by variable charge soils

In the present study, the effect of two substituted benzoic acids on Cu(II) adsorption onto two variable charge soils was investigated, with the emphasis on the adsorption and desorption equilibrium of Cu(II). Results showed that the presence of organic acids induced an increase in Cu(II) adsorption onto the two soils. The extent of the effect was related to the initial concentrations of Cu(II) and organic acid, the system pH, and the nature of the soils. The effect of organic acids was greater for Oxisol than for Ultisol. Phthalic acid affected Cu(II) adsorption to a greater extent than salicylic acid did. The effect of organic acids varied with pH. The adsorption of Cu(II) induced by organic acids increased with increasing pH and reached a maximum value at approximately pH 4.5, and then decreased. It can be assumed that the main reason for the enhanced adsorption of Cu(II) is an increase in the negative surface charge caused by the specific adsorption of organic anions on soils because the desorption of Cu(II) adsorbed in organic acid systems was greater than that for the control. The desorption of Cu(II) absorbed in both control and organic acid systems also increased with increasing pH; it reached a maximum value at pH ∼5.25 for control and salicylic acid systems and at pH ∼5.1 for a phthalic acid system, then decreased. This interesting phenomenon was caused by the characteristics of the surface charge of variable charge soils.     

Applications of the continuous-flow stirred-cell (CFSC) technique: II. The adsorption behaviour of Na, Cs, Sr, Cu, Ni and Pb on humic acids

The first part of this paper deals with the sorption of Na, Cs, Sr, Ni, Cu and Pb on two humic fractions derived from a soil. The sorption data for individual elements were obtained using the continuous-flow stirred-cell (CFSC) technique, in which the metal sorptive solution is pumped through a cell containing a known mass of the humic acid retained by a filter and the solution emerging from the cell was analysed by either atomic absorption spectrometry (Cu, Ni and Pb) or by the combined use of radioisotope dilution and gamma-ray spectroscopy (Na, Cs and Sr). Sorption isotherms were determined at two flow rates. It was found that, in general, the sorption isotherms for all the metals studied could be described by the Langmuir equation and parameters derived from the fitted line provided information on the metal-humate binding strengths and the maximum amount of metal sorbed per unit mass of humic acid. Caesium showed anomalous behaviour at certain flow rates in both its sorption and desorption behaviour. In the second part of the paper we discuss the sequential sorption and desorption of one metal by another on the same humic fraction, using Na, Cs, Zn and Cd. The aim was to elucidate the nature of the binding process when several metals were competing simultaneously for the functional groups on the humic acids. In addition, at the end of the experiment, the humic material was isolated and analysed by gamma-ray spectroscopy to determine the metals still bound in this fraction. Some tentative conclusions concerning the nature of the metal-humate complexes are made on the basis of these data.     

Comparative studies on the delignification of pine kraft-anthraquinone pulp with hydrogen peroxide by binucleus Mn(IV) complex catalysis

Pine kraft-anthraquinone (kraft-AQ) pulp was bleached in alkaline solution with hydrogen peroxide catalyzed by either [L(1)Mn(IV)(micro-O)(3)Mn(IV)L(1)](PF(6))(2)] (C1) or [LMn(IV)(2)(micro-O)(3)] (ClO(4))(2) (C2) at 60 and 80 degrees C for 120 min with a catalyst charge of 10 ppm on pulp. The resulting bleached pulp was hydrolyzed with cellulase to obtain insoluble and soluble residual lignins. The alkaline bleaching effluents were acidified to precipitate alkaline-soluble lignins. These lignin preparations were then characterized by 2D heteronuclear multiple-quantum coherence (HMQC) NMR spectroscopic techniques. The results showed that biphenyl (5-5) and stilbene structures of the residual lignin in the pulp are preferentially degraded in both the C1- and C2-catalyzed bleachings, whereas beta-O-4, beta-5, and beta-beta structures undergo degradation to a lesser extent. In both cases, the degradation of the residual lignin increased with the increase in reaction temperature from 60 to 80 degrees C. Thus, the result of C1-catalyzed delignification is not in agreement with the observed decrease in the disappearance rate for substrates in the C1-catalyzed oxidation of lignin model compounds with hydrogen peroxide when the reaction temperature is increased from 60 to 80 degrees C. In addition, the resulting residual lignins in the C2-catalyzed bleaching at 80 degrees C are less degraded than the corresponding lignins in the C1-catalyzed bleaching at both 60 and 80 degrees C. Thus, C1 is more effective than C2 as catalyst in the binucleus Mn(IV) complex-catalyzed bleaching of pine kraft-AQ pulp with hydrogen peroxide.