Abstract
Purpose
Humic substances (HS) being natural polyelectrolyte macromolecules with complex and disordered molecular structures are a key component of the terrestrial ecosystem. They have remarkable influence on environmental behavior of iron, the essential nutrient for plants. They might be considered as environmental friendly iron deficiency correctors free of synthetic iron (III) chelates disadvantages. The main goal of this study was to obtain water-soluble iron-rich humic compounds (IRHCs) and to evaluate their efficiency as chlorosis correctors.
Materials and methods
A facile preparation technique of IRHCs based on low-cost and available parent material was developed. The iron-containing precursor (ferrous sulfate) was added dropwisely into alkaline potassium humate solution under vigorous stirring and pH-control. A detailed characterization both of organic and inorganic parts of the compounds was provided, the iron species identification was carried out jointly by EXAFS and Mössbauer spectroscopy. Bioassay experiments were performed using cucumber Cucumis sativus L. as target plants. Plants were grown in modified Hoagland nutrient solution, prepared on deionized water and containing iron in the form of IRHCs. Total iron content in dry plants measured by spectrophotometry after oxidative digestion and the chlorophyll a content determined after acetone extraction from fresh plant were used as parameters illustrating plants functional status under iron deficiency condition.
Results and discussion
The high solubility (up to130 g/l) and iron content (about 11 wt%) of the IRHCs obtained allow considering them to be perspective for practical applications. A set of analytical methods has shown that the main iron species in IRHCs are finely dispersed iron (III) oxide and hydroxide nanoparticles. An application of the precursor solution acidification allows to obtain compounds containing a significant part of total iron (up to 30 %) in the form of partly disordered iron (II–III) hydroxysulphate green rust GR(SO4 2−). Bioavailability of iron from IRHCs was demonstrated using bioassay in cucumber plants grown up on hydroponics under iron deficiency conditions.
Conclusions
The application of iron oxides chemistry for humic substance containing solution was proved to be an effective approach to synthesis of IRHCs. Using bioassay on cucumber plants C. sativus L. under iron deficiency conditions, the efficiency of compounds obtained as chlorosis correctors was demonstrated. Application of water-soluble IRHCs led to significant increase of chlorophyll a content (up to 415 % of the blank) and iron content in plants (up to 364 % of the blank) grown up on hydroponics.
Similar content being viewed by others
References
Aguirre E, Lemenager D, Bacaicoa E, Fuentes M, Baigorri R, Zamarreno AM, Garcıa-Mina JM (2009) The root application of a purified leonardite humic acid modifies the transcriptional regulation of the main physiological root responses to Fe deficiency in Fe-sufficient cucumber plants. Plant Physiol Biochem 47:215–223
Álvarez-Fernández A, Garcıa-Marco S, Lucena JJ (2005) Evaluation of synthetic iron(III)-chelates (EDDHA/Fe3+, EDDHMA/Fe3+ and the novel EDDHSA/Fe3+) to correct iron chlorosis. Europ J Agronomy 22:119–130
Anderson CA (1983) The effect of FeEDDHA on the development of lime-chlorosis in two seedling populations of Eucalyptus obliqua L’Herit. Plant Soil 70:299–302
Antonopoulou C, Dimassi K, Therios I, Chatzissavvidis C, Papadakis I (2007) The effect of Fe-EDDHA and of ascorbic acid on in vitro rooting of the peach rootstock GF-677 explants. Acta Physiol Plant 29:559–561
Bar-ness E, Chen Y (1991) Manure and peat based iron-organo complexes. Plant Soil 130:35–43
Bell RW, Dell B (2008) Micronutrients for sustainable food, feed, fibre and bioenergy production. International Fertilizer Industry Association (IFA), Paris
Bitcover EH, Sieling DH (1951) Effect of various factors on the utilization of nitrogen and iron by Spirodela polyrhiza (l.) Schleid.1. Plant Physiol 26:290–303
Chassapis K, Roulia M, Nika G (2010) Fe(III)–humate complexes from Megalopolis peaty lignite: a novel eco-friendly fertilizer. Fuel 89:1480–1484
Chen Y, Clapp CE, Magen H (2004) Mechanisms of plant growth stimulation by humic substances: the role of organo-iron complexes. Soil Sci Plant Nutr 50(7):1089–1095
Chernyshov AA, Veligzhanin AA, Zubavichus YV (2009) Structural materials science end-station at the Kurchatov Synchrotron Radiation Source: recent instrumentation upgrades and experimental results. Nucl Instrum Meth A 603:95–98
Cornell RM, Schwertmann U (2003) The iron oxides, Structure, properties, reactions occurrences and uses. Wiley, Weinheim
Dickson DPE, Heller-Kallai L, Rozenson I (1980) Mossbauer spectroscopic studies of hufiic acid and fulvic acid soil fractions. J de physique Colloque C1(41):c1–409
Hansen EH, Mosbaek H (1970) Mossbauer studies of an iron(III)-fulvic acid complex. Acta Chem Scand 24:3083–3084
Herjsted LN (1991) Process for preparing preferred iron humates. 25.05.1993
Horneer CK, Burk D, Hoover SR (1934) Preparation of humate iron and other humate metals. Plant Physiol Biochem 9:663–669
Kovacs K, Kuzmann E, Fodor F, Vertes A, Kamnev AA (2005) Mössbauer study of iron uptake in cucumber root. Hyperfine Interact 165(1–4):289–294
Lakatos B, Korecz L, Meisel J (1977) Comparative study on the mossbauer parameters of iron humates and polyuronates. Geoderma 19:149–157
Levinskij BV (2002) Method for preparing complex humin fertilizers. Russian Federation Patent 2002
Lobartini JC, Tan KH, Pape C (1998) Dissolution of aluminum and iron phosphates by humic acids. Commun Soil Sci Plant Anal 29(5–6):535–544
Lovley DR, Woodward J, Blunt-Harris E, Hayes L, Phillips E, Coates J (1998) Humic substances as a mediator for microbially catalyzed metal reduction. Acta Hydrochim Hydrobiol 26:152–157
Mahesh K, Sharma ND, Gupta DC (1979) Mossbauer study of iron (III) salycilates. Proc Indian Natl Sci Acad, Part A 45:277–283
Mokronosov AT (1994) The small workshop on plant physiology. Moscow State University, Moscow
Morgan B, Lahav O (2007) The effect of pH on the kinetics of spontaneous Fe(II) oxidation by O2 in aqueous solution—basic principles and a simple heuristic description. Chemosphere 68:2080–2084
Muscolo A, Sidari M, Attinà E, Francioso O, Tugnoli V, Tugnoli V (2007) Biological activity of humic substances is related to their chemical structure. Soil Sci Soc Am J 71:75–85
Nakamoto K (1986) Infrared and raman spectra of inorganic and coordination compounds. Wiley-Interscience, New York
Newville M (2001) IFEFFIT: interactive XAFS analysis and FEFF fitting. J Synchrotron Rad 8(2):322–324
Perez-Sanz A, Lucena JJ, Graham MC (2006) Characterization of Fe–humic complexes in an Fe-enriched biosolid by-product of water treatment. Chemosphere 65:2045–2053
Perminova I (2005) Humic acids metallic compound: preparation thereof, composition, preparation containing samе and use of said compounds. Germany Patent 2005
Polyakov AY, Goldt AE, Sorkina TA, Perminova IV, Pankratov DA, Goodilin EA, Tretyakov YD (2012) Constrained growth of anisotropic magnetic δ-FeOOH nanoparticles in the presence of humic substances. CrystEngComm 14:8097–8102
Refait P, Gehin A, Abdelmoula M, Genin J-MR (2003) Coprecipitation thermodynamics of iron(II–III) hydroxysulphate green rust from Fe(II) and Fe(III) salts. Corros Sci 45:659–676
Ritchie JD, Perdue EM (2003) Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matter. Geochim Cosmochim Acta 67(1):85–96
Romheld V, Merschner H (1986) Evidence for a specific uptake system for iron phytosiderophores in roots of grasses. Plant Physiol 80(1):175–180
Schwertmann U, Cornell RM (2000) Iron oxides in the laboratory preparation and characterization. Wiley, Weinheim
Shenker M, Chen Y (2005) Increasing iron availability to crops: fertilizers, organo-fertilizers, and biological approaches. Soil Sci Plant Nutr 51(1):1–17
Stevenson FJ (1982) Humus chemistry: genesis, composition, reactions. Wiley, New York
Stevenson FJ, Goh KM (1971) Infrared spectra of humic acids and related substances. Geochim Cosmochim Acta 35:471–483
Walsh S, Lappin-Scott HM, Stockdale H, Herbert BN (1995) An assessment of the metabolic activity of starved and vegetative bacteria using two redox dyes. J Microbiol Methods 24:1–9
Yehuda Z, Hadar Y, Chen Y (2003) Immobilized EDDHA and DFOB as iron carriers to cucumber plants. J Plant Nutr 26(10&11):2043–2056
Acknowledgments
The authors thank Dr. Boris N. Tarasevich and Sergey Shuvaev for their help and discussions. This research was supported by RFBR No. 10-03-00803, RFBR No. 11-03-12177, the Program of Development of MSU and the government contract no. 16.552.11.7055 of the Russian Ministry of Education and Science.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Caixian Tang
Rights and permissions
About this article
Cite this article
Sorkina, T.A., Polyakov, A.Y., Kulikova, N.A. et al. Nature-inspired soluble iron-rich humic compounds: new look at the structure and properties. J Soils Sediments 14, 261–268 (2014). https://doi.org/10.1007/s11368-013-0688-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11368-013-0688-0