Macromolecular changes of humic substances induced by interaction with organic acids

Two different humic materials, one from a forest soil and the other from wormcasts, were used to study the influence of mineral and organic acids on the conformational properties of humic substances. The macromolecular changes were followed by low pressure gel permeation chromatography after titrating humic material to low pHs with acids. All organic acids (mono-, di-, tri-carboxylic, and oxy-acids), added to humic solution prior to a gel permeation in an alkaline buffer, were able to shift the totality of absorbance of the humic chromatographic peak from high to low molecular sizes. Mineral acids, phenol, alcohols, dipolar aprotic solvents, could not produce the same shift and gave total absorbance at the column void volume as in the case of humic substances alone. The chromatographic peak shifted back to elution volumes proper of higher size molecules when the humic-organic acid mixture was back-titrated to high _pHs before gel permeation. Elution in a much stronger alkaline buffer did not change the overall macromolecular behaviour. These results suggest that humic substances behave as micelles in solution and that hydrophobic bondings play an important role in holding humic molecules together. The organic acids enter the interior of the humic micelle-like aggregates and alter the stereochemical hydrophobic arrangement of the humic material. In alkaline conditions the negative charges developed disrupt the apparent high molecular size configuration and disperse the humic aggregates into small micelles. Such conformational properties of humic substances appear to be a function of pH and of the concentration of organic acid.     

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.     

Reduction of Cr(VI) by soil humic acids

The rate of hexavalent chromium reduction by a soil humic acid (SHA) was investigated in aqueous solutions where concentrations of Cr(VI), H⁺, and SHA were independently varied. Rate experiments were done with a large excess of SHA over Cr(VI). Rates of reduction depend strongly on [H⁺], increasing with decreasing pH. Typical Cr(VI)-SHA reactions display a nonlinear reduction of Cr(VI) with time that cannot be modelled with simple first- or second-order rate equations. An empirical rate equation is developed for Cr(VI)-soil humic acid reactions over a range of experimental conditions. The model is in part based on a reactive continuum concept developed for soil fulvic acids. The rate equation describing Cr(VI) reduction by SHA is: R= -(k₀+k[H⁺]^1/2)[HCrO₄^?]^1/2X_e^?1, where k₀ is (8·3 ± 1·2) × 10^?12, s^?1k is (2·04 ± 0·05) × 10^?9 l^1/2 mol^?1/2 s^?1, and X_e is the equivalent fraction of SHA oxidized. The rate equation adequately models Cr(VI) reduction in an experiment with [Cr(VI)]₀ four times greater than the maximum concentration used in its derivation. Cr(VI) reduction at pH 3 by two other SHAs can also be modelled using the rate equation. The difference between the rate coefficients for the humic acid and the fulvic acid from the same soil was greater than the difference in the rate coefficients for humic acids from different soils.     

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.     

Methane suppression by iron and humic acids in soils of the Arctic Coastal Plain

Methane–climate interactions are reasonably well understood; the biogeochemical controls on net methane fluxes are less so. Within anoxic soils, alternative electron acceptors such as iron and humic substances influence microbial metabolic function, and thus affect the amount of carbon lost as methane (CH₄). We present three years of data from wet sedge tundra landscapes near Barrow, Alaska that show an inverse relationship between dissolved iron and CH₄ concentrations. We found increasing organic layer thickness related to increases in active layer organic matter content, and decreases in both bulk density and extractable iron. Organic layer depth was also a good proxy for carbon dioxide (CO₂) and CH₄ dynamics, with increasing organic layer depths relating to lower dissolved iron, higher amounts of dissolved CH₄, and lower CO₂:CH₄ ratios in the upper active layer. Net CH₄ fluxes were also significantly suppressed following the experimental addition of iron and humic acids. Iron and humic acid treatment effects were indistinguishable for CH₄ net flux; in contrast, post-treatment CH₄ fluxes were an average of 0.74-fold the control treatment flux rates. These results suggest that in-situ CH₄ production is tied to alternative electron acceptor availability, and that organic layer thickness is a good predictor of biogeochemical controls on CH₄ fluxes in wet-sedge Arctic Alaskan tundra.     

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.     

Iron(III) reduction by natural humic acids: a potentiometric and spectroscopic study

The reduction of iron(III) by natural humic acid (NHA) was studied in aqueous solution as a function of pH, time and iron(III) concentration. The information gained from FTIR and ESR spectroscopies as well as potentiometric data suggests that redox reactions occur at a low pH due to the involvement of phenolic groups and radicals. At pH values higher than 3.5 the reaction is strongly inhibited by the formation of iron(III)–humate complexes.     

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.     

溶液培养条件下腐殖酸对铁异化还原的影响

腐殖酸对土壤和水体环境中铁(Fe)的还原过程有重要影响。本文采用从山西大同风化煤、河南巩县褐煤、云南昆明滇池底泥中提取制备的腐殖酸,通过布置培育试验并接种土壤悬液,研究了不同来源的腐殖酸对无定形氧化铁异化还原的影响。结果表明:单独添加腐殖酸对氧化铁的还原几乎没有影响;而当同时添加腐殖酸与葡萄糖时,培养基质中氧化铁的还原过程显著加强;腐殖酸浓度越高对氧化铁还原的促进作用越明显。不同来源的腐殖酸因其复杂程度和结构不同,对氧化铁还原的促进作用有明显差异,其中山西大同风化煤提取的腐殖酸促进作用最大,云南昆明滇池底泥和河南巩县褐煤提取的腐殖酸之间则无显著差异。     

溶液体系中非生物因素对胡敏酸还原汞的影响

As a global pollutant process,the reduction of mercury(Hg)is especially important.One pathway is through an abiotic reduction with humic acids(HAs),which is controlled by different factors,including initial Hg and HA concentrations,pH,temperature and light.In this study,three humic acids were selected to illustrate the Hg~(2+)abiotic reduction mechanisms by HAs,and to identify the key limiting factors for reduction rates and amounts.In addition,the initial status of the HAs as a solid or in an aqueous solution were also compared,to help explain why HAs show different dominant characteristics(e.g.complexation or reduction)in the reaction process with Hg.Results indicated that HAs were able to reduce Hg abiotically.Higher initial Hg,higher HA concentrations and either high(8.1)or low(3.6)solution pH decreased the HA reduction capacity.In addition,Hg°production rates increased with increasing temperature,and the same trend was observed with light exposure.Humic acids added as an aqueous solution resulted in significantly greater Hg°production than addition as a bulk solid.Finally,the Hg reduction rate and capacity varied significantly(P0.05)with HAs from different sources.These findings helped to explain why HAs showed different dominant characteristics(e.g.complexation or reduction)in the reaction process with Hg,and evidentially demonstrated the existence of a possible pathway of Hg~(2+)reduction,which indicated that humic substances in natural environments,especially in water bodies,could act either as a sink or a source for Hg.     

Catalytic synthesis of humic acids from phenolic compounds by Mn(IV) oxide (Birnessite)

Abstract

Extract

Humic acids are natural organic polymers and are important constituents of soils (Kononova 1966). Although the mechanisms of the formation of humic acids are very complicated, the oxidative polymerization of polyphenols is considered to be one of the most important mechanisms (Kononova 1966; Stevenson 1982). The oxidative polymerization can be accelerated by enzymes (e.g., Haider et al. 1975; Flaig et al. 1975) as well as by inorganic components (e.g., Kyuma and Kawaguchi 1964; Shindo and Huang 1982; Kumada 1987). Shindo and Huang (1985) and Shindo and Higashi (1986) compared the relative effectiveness of several oxides, primary minerals, and clay minerals in promoting the synthesis of humic polymers from hydroquinone, and found that the promoting effect of Mn(IV) oxide was most striking among the inorganic components studied. The catalytic power of inorganic components in the synthesis of humic polymers from phenolic compounds may be influenced by the chemical structure of the compounds. However, little information is available on this aspect.     

Conformational changes of humic substances induced by some hydroxy-, keto-, and sulfonic acids

We studied the effect of organic acids of plant, microbial, or anthropic origin on the molecular size distribution of dissolved humic acids (HAs). High Performance Size Exclusion Chromatography (HPSEC) was used to evaluate size changes in four different HAs upon addition of hydroxy- (glycolic and malic), keto- (glyoxylic), and sulfonic (benzenesulfonic and methanesulfonic) acids. All humic substances showed a decrease of peaks absorbance when the pH of HAs dissolved in HPSEC mobile phase was lowered from 7 to 3.5 by acid addition before analysis. This effect, combined with an increase of peaks elution volumes in most cases, was interpreted as a disruption of supramolecular humic associations into smaller-size but energy-richer conformations brought about by the formation of mixed intermolecular hydrogen bonding upon acid treatment. The extent of size variation was related to the pKa of acids and also to the chemical and stereochemical affinity of humic components with the chemical structure of the acids. Dicarboxylic malic acid was the most effective in modifying humic conformations in all HAs whereas the aromatic-rich superstructure of HA from an oxidized coal was effectively disrupted by the relatively small methanesulfonic acid and the chemically akin benzenesulfonic acid. These results suggest that the conformational association of humus dissolved in the soil solution may be systematically altered by organic acids present in the rhizosphere and might have effects on plant and microbial activities.     

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).     

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.     

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.