Humic substances in acid organic soils: modelling their release to the soil solution in terms of humic charge

Batch titration experiments were carried out with organic soil samples in order to investigate the release to the solution phase of humic substances (HS). Measurements were made of pH, dissolved organic carbon (DOC) concentration, and the concentration of mono-meric (inorganic + organic) aluminium, as functions of added acid or base. DOC was taken to be entirely due to HS. The results can be interpreted in terms of a model in which the soil is considered to contain two types of HS–mobile or potentially mobile (HSM), and immobile (HSI). The binding of inorganic ions by the HS is calculated using humic ion-binding model IV, previously developed in this laboratory. Model IV allows the charges on the HS (Z_HSM, Z_HST) to be calculated; these are determined mainly by the binding of H+ and A13+. Concentrations of HS in solution, [HS_aq], are given by the equation: where |Z_HSM| is the modulus of Z_HSM, n_HSM is the carboxyl group content of HSM, c_HSM is the soil content of HSM, β is a fitting parameter, and square brackets, [ ], indicate concentrations. For most of the soils a value for β of 3 gives acceptable agreements between measured and calculated values of [HS_aq], indicating a major influence of charge on release. The optimized value of c_HSM differs considerably among soils, whereas c_HIS varies by only a factor of about two. Total humic contents (c_HSM+ c_HSI estimated by model optimization are in approximate agreement with values estimated by extraction of the soils with NaOH.     

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).     

Nature of soil carbohydrate and its association with soil humic substances

The fulvic acid and alkali-soluble polysaccharide fractions of a sandy loam arable soil of the Countesswells series have been subjected to acid hydrolysis or methylation and the products examined by infra-red and NMR spectroscopy, pyrolysis mass spectrometry and chemical analysis. Infra-red and NMR spectroscopy of the polysaccharide fraction indicated that the substance was predominantly carbohydrate, although sugars accounted for less than one-third of the weight by chemical analysis. Pyrolysis mass spectrometry con-firmed the presence of sugars by sugar anhydride formation, but also showed the presence of ‘secondary’ or ‘pseudo’ polysaccharide. The fulvic acid contained only 2–3% sugars by chemical analysis, whereas a much larger carbohydrate component was suggested by physicochemical analyses. Infra-red and pyrolysis mass spectrometry difference spectra for the residues after acid hydrolysis indicated the release of material with some of the characteristics of glycoprotein. Most of the carbohydrate present in the fulvic acid was of the secondary or pseudo polysaccharide type. The hypothesis that the secondary polysaccharide could be a degraded polysaccharide structure in which some sugar residues have been partly transformed to melanoidins by Maillard reaction is explored.     

Influence of soil humic substances and herbicides on the growth of pea (Pisum sativum L.) in nutrient solution 1

No morphological and length modifications of the root and shoot systems are apparent in pea (Pisum sativum L.) plants of three varieties grown in the presence of 100 mg/L humic acid or fulvic acid or 20 mg/L linuron [3‐(3,4‐dichlorophenyl)‐l‐methoxy‐l‐methylurea] or ametryne [2‐ethylamino‐4‐iso‐propylamino‐6‐methylthio‐1,3,5‐triazine]. A combination of humic substance and herbicide at these concentrations produces in all pea varieties a differentiated and marked reduction in root length and large morphological alterations of roots. Statistical analysis of data show that differentiated and highly significant or significant effects are produced on the shoot and root dry weight by either the humic substance or herbicide alone, and by any combination of two or three factors considered (variety, humic substance, herbicide).     

Aluminum speciation in the bulk and rhizospheric soil solution of the species colonizing an abandoned copper mine in Galicia (NW Spain)

Purpose  

The present study was carried out to identify and quantify the aluminum species present in the bulk and rhizospheric soil solution of the spontaneous vegetation colonizing the dump (Calluna vulgaris, Erica cinerea) and slope (C. vulgaris, E. cinerea, Salix atrocinerea) of an abandoned Cu mine in Touro (Galicia, NW Spain).     

An appreciation of the contribution of Frank Stevenson to the advancement of studies of soil organic matter and humic substances

Purpose

The aims of this paper are to outline the state of knowledge with regard to the chemistry of soil organic matter (SOM) prior to 1950; then, to review and evaluate the contributions made by Frank Stevenson during Stevenson’s research period (1950–1994); and subsequently to outline advances that are being made in the modern era.

Progress in the Stevenson period

Frank Stevenson’s research career began in the middle of the twentieth century when a number of techniques of colloid chemistry were available to him, but relatively few of the recently developed instrumental techniques and other procedures of analytical organic chemistry that have enabled significant advances to be made in the chemistry and properties of SOM components.The contributions that Frank Stevenson has made to the chemistry of SOM and of humic substances (HSs) are an integral part of his book (first and second editions) Humus Chemistry: Genesis, Composition, Reactions. The validity of the terms humus and HSs are being questioned as legitimate terms that describe definable components, and SOM is being viewed as a ‘continuum of progressively decomposing organic compounds’. The legitimacy of isolating the organic matter components from their native soil environment is questioned. Those who pose such questions would do well to consider how progress could have been made in the vital life sciences areas of, for example, proteomics and genomics, without the isolation of the relevant cellular components. We recognise the importance of clear and rigorous definitions of HS components and stress the need to isolate these components from the SOM matrix as a prerequisite to the study of the composition, structure and reactivity of these components. We disagree with proposals or suggestions that do not recognise HSs as a scientific entity, and we feel sure that Frank Stevenson would have supported this stance. Various studies of SOM and of HSs have taken place over the centuries, but progress was slow because the tools required to study such complex systems were not available. Frank Stevenson’s research involved many areas of humic chemistry, and his major advances were in aspects of functionality and in the interactions of humic functional groups with metals and to a lesser extent with anthropogenic organic chemicals. His studies of nitrogen and of ammonia in relation to organic matter also had a very great impact.

Progress in the modern era

Frank Stevenson can be said to have provided the stimulation that enabled beginners and established scientists to obtain a good grasp of the fundamentals of SOM and the humic sciences. His scientific contributions have catalysed many of the significant advances that have been made in the field since he retired. In the final section, some of the advances that have been made using modern analytical techniques are addressed and some of the controversial topics that have recently arisen are discussed.

     

A comparative survey of recent results on humic-like fractions in organic amendments and effects on native soil humic substances

The main scope of the wide use of organic amendments of various origin and nature in modern agriculture is to increase and/or restore the organic matter content in organically poor or depleted soils in order to maintain and/or increase crop production and reduce soil exposure to degradation, erosion, desertification and pollution. The agronomically efficient and environmentally safe use of any organic amendment requires, however, an adequate control not only of the chemical quality of the humic substance (HS)-like fractions contained, which is an important indicator of the maturity and stability achieved by organic matter in the amendment, but also of the effects that these HS may have on native soil HS. In this review, the most recent results obtained on this topic by the research groups operating in Bari, Italy, and in Madrid, Spain, are discussed comparatively with results recently published by other research groups. Overall, HS-like components of organic amendments are characterized by higher aliphatic character and molecular heterogeneity, lower contents of O, acidic functional groups and organic free radicals, and lower degrees of aromatic ring polycondensation, polymerization and humification than native soil HS. These differences are less evident for composted materials. The composition, structure and functionalities of HS in amended soils may be affected in different ways and at various extents on dependence of the nature, origin and rate of amendment. In general, these properties are intermediate between those of the unamended soil HS and the HS-like fractions in the amendment, but generally resemble more the former than the latter, especially with increasing time after amendment application.     

Sorption and degradation of azimsulfuron on iron(III)-rich soil colloids

The sorption of N-[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide (AZS) on an iron oxide, iron(III)-humate, and an Fe3+-saturated clay was studied using a batch equilibrium method. Generally, 20 mg of each colloid was equilibrated with 20 mL of AZS solution (1.5-12.7 microM). The sorption on iron-montmorillonite and iron oxide was rapid, and the equilibrium was attained within 1.5 and 5 h, respectively. In the case of Fe-saturated humic acid the equilibrium time was 20 h. After equilibration, the phases were centrifuged (19000g, 15 min) and the supernatant was sampled and analyzed by HPLC. The values of Freundlich constants indicate that iron oxide (Kads = 199.5) shows the highest sorptive capacity toward AZS, followed by iron(III)-clay (Kads = 146.6) and iron(III)-humate (Kads = 108.2). With elapsing time, AZS degradation was observed in all colloidal suspensions. Iron-humate (t(1/2) = 136 h) is most effective in promoting AZS degradation, followed by iron oxide (t(1/2) = 204 h) and iron-clay (t(1/2) = 385 h). The metabolites 2-amino-4,6-dimethoxypyrimidine and 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide, arising from a hydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. A Fourier transform infrared study suggests that the sorption of AZS on iron-clay involves the protonation of one of the two basic pyrimidine nitrogens induced by the acidic water surrounding the saturating Fe3+ ions. Instead, the formation of a six-membered chelated complex favors the sorption of AZS on iron oxide.     

Atrazine photodegradation in aqueous solution induced by interaction of humic acids and iron: photoformation of iron(II) and hydrogen peroxide

The photochemical formation of Fe(II) and hydrogen peroxide (H 2O 2) coupled with humic acids (HA) was studied to understand the significance of iron cycling in the photodegradation of atrazine under simulated sunlight. The presence of HA significantly enhanced the formation of Fe(II) and H 2O 2, and their subsequent product, hydroxyl radical ( (*)OH), was the main oxidant responsible for the atrazine photodegradation. During 60 h of irradiation, the fraction of iron presented as Fe(II) (Fe(II)/Fe(t)) decreased from 20-32% in the presence of the Fe(III)-HA complex to 10-22% after adding atrazine. The rate of atrazine photodegradation in solutions containing Fe(III) increased with increasing HA concentration, suggesting that the complexation of Fe(III) with HA accelerated the Fe(III)/Fe(II) cycling. Using fluorescence spectrometry, the quenching constant and the percentage of fluorophores participating in the complexation of HA with Fe(III) were estimated by the modified Stern-Volmer equation. Fourier transform infrared spectroscopy (FTIR) offered the direct evidence that Fe(III)-carboxylate complex could be formed by ligand exchange of HA with Fe(III). Based on all the information, a possible reaction mechanism was proposed.     

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.     

Effects of temperature on soil organic carbon fractions contents,aggregate stability and structural characteristics of humic substances in a Mollisol

Purpose

Under a global warming scenario, understanding the response of soil organic carbon fractions and aggregate stability to temperature increases is important not only for better understanding and maintaining relevant ecosystem services like soil fertility and crop productivity, but also for understanding key environmental processes intimately related with the maintenance of other regulatory ecosystem services like global climate change mitigation through carbon sequestration. An increase in temperature would accelerate the mineralization of soil organic carbon. However, the properties of organic carbon remained in soil after mineralization is not well known.

Materials and methods

Mollisol was collected at 0–20-cm depth from maize (Zea mays L.) field in Northeast China. A 180-day incubation experiment was conducted at three different temperatures (10, 30, and 50 °C) under constant soil moisture (60 % water holding capacity). Soil samples were assayed for total organic carbon (TOC), water-soluble organic carbon (WSOC), easily oxidizable organic carbon (EOC), humic fractions carbon, aggregate-associated carbon, and water stability of aggregates. Elemental analysis and solid-state ¹³C nuclear magnetic resonance spectroscopy were used to characterize humic acid and humin fractions.

Results and discussion

The contents of soil TOC, EOC, humic fractions carbon, and aggregate-associated carbon decreased with the increase in temperature. The proportion of 2–0.25-mm macroaggregate and the mean weight diameter (MWD) of aggregates also decreased. The C, H, N, S, alkyl C, and O-alkyl C contents of humic acid and humin decreased, whereas the O, aromatic C, and carbonyl C contents increased. The H/C, aliphatic C/aromatic C, and O-alkyl C/aromatic C ratios in humic acid and humin fractions decreased.

Conclusions

The increase in temperature has a negative impact on soil organic carbon content, soil aggregation, and aggregate stability. Moreover, humic acid and humin molecules become less aliphatic and more decomposed with the increase in temperature.

     

Residual leachability of CCA-contaminated soil after treatment with biodegradable chelating agents and lignite-derived humic substances

Purpose

The aim of this study was to enhance the soil remediation of timber treatment sites; the potential application of biodegradable chelating agents and humic substances as enhancing agents was assessed in terms of the residual leachability of chromium, copper and arsenic (CCA).

Materials and methods

This study applied four leachability tests on a field-contaminated soil after 48-h washing with ethylenediamine-N,N-disuccinic acid (EDDS), glutamic-N,N-diacetic acid, ethylenediaminetetraacetic acid and humic substances derived from lignite and two other sources.

Results and discussion

It was noteworthy that the reduction in the total metal concentrations after soil washing was not predictive of the leaching behaviour. When assessed by toxicity characteristic leaching procedure (TCLP) and waste extraction test (WET), Cu and As leachability was decreased as a result of their extraction by soil washing. By contrast, when assessed by synthetic precipitation leaching procedure (SPLP) and European Council Waste Acceptance Criteria (ECWAC) tests, Cu and As leachability was found to increase, probably because the effect of destabilization of residual metals during soil washing was more observable in unbuffered leaching solutions. On the other hand, Cr leachability was acceptably low in TCLP and WET but still exceeded drinking water standard in SPLP and ECWAC tests.

Conclusions

The three chelating agents were able to meet the criteria for Cu in all leachability tests, while the limits of As concentrations could only be met by EDDS in TCLP test. The three humic substances reduced the leachate concentrations of Cu and As without destabilizing the residual metals; however, the reduction was insufficient to meet the required limits in all leachability tests considered.     

The effect of humic acids and their complexes with iron on the functional status of plants grown under iron deficiency

The effect of humic acids (HAs) and their iron complexes (Fe–HAs) on the input of the main mineral elements into wheat seedlings, as well as on the efficiency of photosynthesis and the lipid profile of plants, under iron deficiency has been studied. The input of iron from Fe–HA complexes and its predominant accumulation in roots are demonstrated. It is found that HAs increase the efficiency of photosynthesis due to enhanced electron transport in photosystem II. It is shown that the application of HAs and Fe–HAs is accompanied by an enhanced input of Zn into plants, which could increase the antioxidant status of plants under iron deficiency conditions. In addition, a pronounced increase in the content of lipids in plants is revealed, which is indicative of the effect of HAs on plant metabolism. The obtained results suggest that the positive effect of Fe–HAs and HAs on plants under iron deficiency conditions is due to a combination of factors, among which the effect of HAs on the antioxidant status of plants and the plant lipid metabolism predominates.     

Role of inorganic anions in the structural transformation of molecules of humic substances in soil

It was shown that inorganic anions of exogenic compounds affected the structure of humic and fulvic acids in gray forest soil, as well as the yield of humic acids and their contents of carbon and metals. Humic substances in arable soil more readily interacted with the anions of extractants and fertilizers compared to virgin soil. Changes were revealed in the energy state of the electronic system of P- and N-modified fragments of humic acids from the arable soil. New ligand groups and chelate nodes were found in modified fragments using differential electronic spectra.     

On the components of soil humic acids (part 9)

The carbohydrates in soil organic matter seem to be derived from undecomposed or partially decomposed plant and microbial residues, In soil, these carbohydrates exist chiefly in such from as polysaccharide hemicellulose, and their polyuronide has been the chief object of investigation^1)-3). In various soil, the polyuronide is found in a large quantity in fulvic fraction of soil organic matter and has been considered as important in connection with the physical structure of soil^4),5). According to Lynch ⁵⁾, the carbohydrate content of humic acid is markedly smaller than that of fulvic acid. His work also indicates that a' considerable change is noted in the content and composition of the carbohydrate in humic acid because of the addition of some organic substances to the soils, or of the cultivation of virgin soils. Further, some investigators⁷⁾ believe that uronic acid is introduced into the aromatic structure of the humic acid by changing into pentose and furan. Accordingly, it seems that the role of carbohydrate in the formation of soil humic acid should not be overlooked.     

Solubilization of Fe (III) from humic-Fe complexes,humic/Fe-oxide mixtures and from poorly ordered Fe-oxide by organic acids - consequences for P adsorption

The effect of organic acids on the solubility of Fe from humic Fe complexes, poorly ordered Fe-oxides and humic/Fe-oxide mixtures was investigated at pH 4 and 7. After reaction, the suspensions were filtered through a 20 000 D membrane and Fe and humic concentrations were determined in the filtrate. Among four organic acids, citric acid had the strongest effect on Fe-solubility and solubilized up to 25% of total Fe from the humic complexes at pH 4. Humic substances were solubilized by citrate too, the proportions being higher at pH 7 than at pH 4. Malic and tartaric acid solubilized substantial but lower amounts of Fe from humic complexes than citric acid, whereas phthalic acid did not solubilize Fe and humics. Citrate added to poorly ordered Fe-oxide and its mixtures with humics, aged for 65 days, increased 20 000 D filtrable Fe, the effect being higher for humic/Fe-oxide complexes. Adding citrate to humic/Fe-oxide mixtures and to Fe-oxide strongly decreased the P sorption, the extent, being higher for the former adsorbent.     

Gallium(III) does not actively substitute for iron(III) in iron/gallium competition studies

Strategy II plants respond to Fe stress by releasing a phytosiderophore and are believed to absorb Fe as Fe(III). Gallium(III) has chemical characteristics which have made it useful as a substitute for Fe(III) in biological systems. The objectives of our study were to: 1) determine if Ga(III) acts competitively to reduce Fe(III) uptake or otherwise substitutes for Fe(III) in barley (Hordeum vulgare L.), and 2) determine if the competition for Fe(III) between EDDHA or BPDS and barley further elucidates the form of Fe absorbed by barley. Chlorosis ratings, phytosiderophore production, and tissue Fe contents were indexes of Fe stress.

Gallium was absorbed and translocated by the plant both in the presence and absence of Fe, and slightly alleviated Fe stress in the absence of Fe. However, Fe uptake was not affected by the presence of Ga. Thus, Ga(III) did not seem to compete with Fe(III) for uptake. Increasing EDDHA in solution intensified chlorosis and phytosiderophore production and reduced root Fe, but did not reduce leaf Fe concentration. Increased BPDS had no influence on either chlorosis or leaf Fe, but did cause phytosiderophore production to increase and root Fe to decline. The presence of Fe(II) in solutions containing BPDS suggests a potential for reducing Fe(III) in the roots of barley.     

The involvement of iron and aluminum in the bonding of phosphorus to soil humic acid

Abstract

With a peat soil similar amounts of phosphorus (P) were coprecipitated with humic acid from alkali extracts over a limited range of strongly acidic pH, whereas with a mineral soil the amount was pH dependent. The difference between the two soils relates to the much greater total amounts of inorganic P and aluminum (Al) present in the extract of the mineral soil. In this acid mineral soil, Al rather than iron (Fe) may be involved in the formation of metal bridges in humic acid‐metal‐inorganic P complexes. Neither Al or Fe were implicated in binding of organic P to humic acid. The P species observed in humic acids was dependent on the pH at which they were precipitated from the alkali extracts. In the peat soil the inorganic P was an order of magnitude lower than the organic P.     

Molecular composition of humic substances in tundra soils (13C-NMR spectroscopic study)

Functional groups and molecular fragments of humic substances (HSs) from cryohydromorphic peat gley tundra and surface-gley tundra soils have been identified by ¹³C-NMR spectroscopy. The analysis of HS preparations has shown that the molecules of humic acids (HAs) are enriched with aromatic fragments compared to fulvic acids (FAs). Aliphatic chains, carbohydrate- and amino acid-type structures prevail in the carbon skeleton of the FAs. An integrated parameter of the HS hydrophobicity has been proposed. The parameter represents the total portion of unoxidized carbon atoms and allows indirectly assessing the amphiphilic properties of HSs.     

Effect of temperature on the decomposition of organic substances in flooded soil

In discussing the seasonal and locational difference in the metabolism of rice soil, it is of primary necessity to know how various reactions in soil are changed by temperature.