The interaction of different components of organic carbon with varying forms of iron and aluminum in soils with andic properties treated with humic acid

Document Type : Research Paper

Authors

1 Soil Science Department, Faculty of Agriculture, University of Tehran, Karaj, ran

2 Soil Science Departmen, Faculty of Agriculture, University of Tehran, Karaj, Iran

Abstract

Organic-mineral complexes, which are mainly the result of the interaction of organic and mineral soil materials, are one of the most important factors influencing the carbon cycle and soil functions. This study aims to investigate the role of allophanic minerals, and different forms of soil iron and aluminum in stabilizing input organic carbon. Organic carbon components and different forms of iron and aluminum were measured before and after treating the twelve soil samples with andic properties, with humic acid for six months under laboratory conditions. The results showed that the stabilization of organic carbon is mainly controlled by the formation of organic-mineral complexes, and the allophanes. The formation of surface complexes between bonding agents on the surfaces of mineral and organic materials is one of the most important processes of organic material stabilization in soil. Aluminum and/or iron-humus complexes are another important factor in stabilizing soil organic matter. Stabilization and complex formation with organic materials, allophanes, amorphous iron and aluminium (Feo, Alo), play the most important role in stabilizing organic materials. Comparison of oxalate extractable silica and iron (Feo, Sio); Pyrophosphate extractable (Alp, Fep), and total iron (Fet) (p<0.05) indicated a significant difference between the treated and control samples. The addition of humic acid, by forming insoluble organic complexes with mineral surfaces on the one hand, and with aluminum and iron released in the soil on the other hand, has caused more stabilization of organic carbon in the soil. The formation of cationic bridges between the electric charge of humic acid functional groups, with allophanes, and the formation of stable organic-metallic complexes has prevented the extraction of iron and aluminum by ammonium oxalate or sodium pyrophosphate.

Keywords

Main Subjects

Introduction

Soil organic carbon is one of the most important elements that affect the quality, element cycles, and other soil functions. The ability of soils to stabilize organic matter (OM) varies depending on their inherent characteristics and management. The characteristics involved in the stabilization of OM are mainly related to the physical, chemical, and biological interactions between the soil's inorganic and organic phases. Organo-mineral complexes are mainly formed by organic materials and from the interaction of materials such as humus with minerals.  Soil with andic properties can store high amounts of organic matter (OM) thanks to the presence of poorly crystalline minerals (Allophane, Imoglite, Fe, and Al Oxy-Hydroxid) that provide large surfaces for the adsorption of organic molecules. However, little is known about the mechanisms involved in the stabilization of OM in soils in arid-semiarid zones. This study aimed to investigate the effect of using Humic Acid on 1) The possibility of using short-range order minerals (Allophane) and different forms of iron and aluminum in stabilizing organic substances. 2) The physical and chemical properties in soils with andic properties.

Material and methods

The 12 soil samples were selected and physical and Chemical analysis were performed. Feo, Alo, Sio, Fep, Alp, Fed and Fet were measured. Allophane content was estimated. Samples were treated sequentially with NaOCl and HF and after each step the amount of organic matter (fractions) were calculated. To treat the soils with humic substances, humic acid was added to each soil sample (70% FC). The samples were then incubated at a constant temperature of 25ºC for 180 days. At the end of the incubation period SOC, Feo, Alo, Sio, Fep, and Alp, were determined again.

Results and discussion

The results indicated that the high reactive specific surface area of allophanes was likely responsible to the high SOM contents, as suggested by the correlation coefficient (r=0.881), while a minor role was played by poorly crystalline Fe (Feo) with an important role in organo-metal complexation, and none by free Al forms. The treatment with NaOCl induced the release (remove) of 5.65 to 20.65 g C kg-1 of soil, Higher amounts of C were released from the clay poorest horizons (r=-0.696, p<0.01). The mineral-associated C (i.e. the amounts released by HF) ranged from 2.9 to 10.8 g kg-1, no depending on the clay contents (r= - 0.146). There are no significant relationships between Mineral-associated OM (removed by HF) and mineral phase properties showing that SOC haven’t any interactions with polymeric Fe and Al (hydroxides) and poorly crystalline minerals (ferrihydrite, allophane, microcrystalline gibbsite). A good indicator of the amounts of the recalcitrant fraction was indeed the untreated soil C/N ratio (r=0.793, p<0.01). While the proportion of recalcitrant C was positively correlated to Sio (r=0.654, p<0.05) and allophanes (r=0.868, p<0.01), it was negatively correlated with Alp (r=-0.762, p<0.05). showed that the ligand exchange reaction on variable-charged minerals is the primary controlling mechanism leading to the stabilities of OC. Also, studies have shown that allophane contains high concentrations of SOM that is resistant to chemical oxidation. The results indicated that the application of three different contents of the HA used in this study had a significant effect (p<0.05) on the extractable Sio and Alp, Feo, Fep, and Fet contents.

Conclusion

The study results demonstrated at first, the most important process for soil organic matter stabilization is the formation of the surface complexes between minerals hydroxyl and the carboxyl groups of organic substances, that mainly controlled by high amounts of short-range-order minerals (allophane). Secondly, poorly crystalline iron (Feo) has a greater effect than Alo, and in acidic soils (without allophane), crystalline iron oxides (ferrihydrite) is more important in soil organic carbon stabilizationthe addition of organic substances prevents the dissolution of organo-mineral complexes. On the other hand, the decomposed and degraded Al and Fe formed organo-mineral complexes by absorbing the positive charge of the functional groups on the humic acid surface. Formation of cation bridges (organo-metal complexes) caused the retention of Al and Fe in the soil and prevented their release by Ammonium oxalate or sodium-pyrophosphate.

Author Contributions

Mohammad Ali Monajjem: Methodology, software, data curation, writing-original draft preparation, formal analysis, writing-review and editing.

Ahmad Heidari: Conceptualization, methodology, software, data curation, validation, writing-review and editing, supervision, project administration and funding acquisition.

All authors have read and agreed to the published version of the manuscript.

Data Availability Statement

Data is available on reasonable request from the authors.

Acknowledgements

The authors would like to thank the reviewers and editor for their critical comments that helped to improve the paper. The authors gratefully acknowledge the support and facilities provided by the Department of Soil Science, University of Tehran, Iran.

Ethical considerations

The authors avoided data fabrication, falsification, plagiarism, and misconduct.

Conflict of interest

The author declares no conflict of interest.

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Iranian Journal of Soil and Water Research
Volume 56, Issue 4
July 2025
Pages 899-917

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