Effect of different kinds of Humic and Fulvic Acids on the release of Manganese from calcareous soils

Document Type : Research Paper

Authors

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

2 Ph.D Graduate, Department of Soil Science and Engineering, Faculty of Agricultural Engineering and Technology, University of Tehran, Iran

3 Soil and Water Research Institute, Agricultural Research, Education, and Extension Organization, Karaj, Iran

Abstract

 
One of the limiting factors in crop yield in calcareous soils of arid and semi-arid regions is the deficiency of micronutrients in these soils. This study was conducted to examine the effects of various commercial humic acids (HAs) and fulvic acids (FAs) on the release of manganese (Mn) in 15 calcareous soils. The results indicated that the application of all five different HAs used in this study had no significant effect (P<0.05) on the release of Mn, but the effects of FAs varied in different soils, the majority of them resulted in a significant increase (P<0.05) in Mn release. In 20% of the soils, either three or all five FAs, and in 26.7 % of the soils, either two or four of the FAs resulted in a significant increase in Mn release. In one soil, none of the FAs were effective in increasing Mn release. Two FA samples, FA1 and FA5, were much more efficient in releasing Mn, indicating that the effectiveness or ability of the marketed or commercial FAs to release Mn, on an equal weight basis, is not the same and varies greatly among them. The difference was, to some extent, due to the ability of these humic substances to form strong (multidentate) complexes with Mn or act as a chelating agent. The results also indicated that effectiveness was dependent on soil characteristics, which were related to the binding strength of Mn with surface functional groups of soils and the solubility of Mn minerals in the soil.

Keywords

Main Subjects


Effect of Different Kinds of Humic and Fulvic Acids on the Release of Manganese from Calcareous Soils

EXTENDED ABSTRACT

 

Introduction:

One of the limiting factors in crop yield in calcareous soils of arid and semi-arid regions is the deficiency of micronutrients, including manganese (Mn), in most of these soils. In arid and semi-arid regions, the micronutrient deficiency is intensified due to the deficiency of soil organic matter, and high  and pH levels. Soil organic matter can play a key role in controlling the mobility of metals. Humic substances are part of soil organic matter. Today, many organic humic products are available worldwide for agricultural use. The reason for the widespread use of humic substances in commercial fertilizers is their ability to increase the availability of nutrients, especially micronutrients and phosphorus.

Purpose:

This study was conducted to examine the effects of ten commercially available, purified humic and fulvic acids with different structures on Mn release in 15 calcareous soils with various physico-chemical properties.

Research method:

In this study, five humic acids and five fulvic acids with different structures were selected. Then FTIR infrared spectroscopy and CHNOS elemental analysis of the humic and fulvic acids were performed. A total of 15 soil samples were selected, which differed not only in their physical and chemical properties, but also in their available Mn content. To treat the soils with humic substances, one mL of 1% humic acid or fulvic acid solution was added to each soil sample and then the moisture content of all soil samples was adjusted to 40% of the saturation percentage by adding distilled water. Untreated soils were also included in the experiment as controls. The samples were then incubated at a constant temperature of 20 ºC for two weeks. At the end of the incubation period, the Mn content of the soil samples was extracted using 1 M sodium acetate solution buffered at pH=8.2. Manganese concentration in soil extracts was determined by flame atomic absorption spectrometry (Perkin Elmer 1100).

Results:

The results indicated that the application of all five different HAs used in this study had no significant effect (P<0.05) on the release of Mn, but the effects of FAs varied in different soils, the majority of them resulted in a significant increase (P<0.05) in Mn release. In 20% of the soils, either three or all five FAs, and in 26.7 % of the soils, either two or four of the FAs resulted in a significant increase in Mn release. In one soil, none of the FAs were effective in increasing Mn release. Two FA samples, FA1 and FA5, were much more efficient in releasing Mn, indicating that the effectiveness or ability of the marketed or commercial FAs to release Mn, on an equal weight basis, is not the same and varies greatly among them. The difference was, to some extent, due to the ability of these humic substances to form strong (multidentate) complexes with Mn or act as a chelating agent. The results also indicated that effectiveness was dependent on soil characteristics, which were related to the binding strength of Mn with surface functional groups of soils and the solubility of Mn minerals in the soil.

Conclusion:

The study results demonstrated that the effectiveness of humic substances on the release of Mn in calcareous soils depends on factors such as the type of humic substances (humic acid or fulvic acid), the source (different structural and chemical properties) and the type of soil.

Ampong, K., Thilakaranthna, M. S., & Gorim, L. Y. (2022). Understanding the role of humic acids on crop performance and soil health. Frontiers in Agronomy4, 848621. https://doi.org/10.3389/fagro.2022.848621
Capasso, S., Chianese, S., Musmarra, D., & Iovino, P. (2020). Macromolecular structure of a commercial humic acid sample. Environments, 7(4), 32.
Chen, H., Koopal, L. K., Xiong, J., Avena, M., & Tan, W. (2017). Mechanisms of soil humic acid adsorption onto montmorillonite and kaolinite. Journal of Colloid and Interface Science, 504, 457-467. https://doi.org/10.1016/j.jcis.2017.05.078
Chen, Y., Senesi, N., & Schnitzer, M. (1978). Chemical and physical characteristics of humic and fulvic acids extracted from soils of the Mediterranean region. Geoderma20(2), 87-104. https://doi.org/10.1016/0016-7061(78)90037-X
Dane, J. H., & Topp, C. G. (Eds.). (2020). Methods of soil analysis, Part 4: Physical methods (Vol. 20). John Wiley & Sons.
Davey, M. P., Berg, B., Emmett, B. A., & Rowland, P. (2007). Decomposition of oak leaf litter is related to initial litter Mn concentrations. Botany85(1), 16-24. https://doi.org/10.1139/b06-150
de Castro, T. A. V. T., Berbara, R. L. L., Tavares, O. C. H., da Graca Mello, D. F., Pereira, E. G., de Souza, C. D. C. B., ... & García, A. C. (2021). Humic acids induce a eustress state via photosynthesis and nitrogen metabolism leading to a root growth improvement in rice plants. Plant Physiology and Biochemistry162, 171-184. https://doi.org/10.1016/j.plaphy.2021.02.043
Donisa, C., Mocanu, R., & Steinnes, E. (2003). Distribution of some major and minor elements between fulvic and humic acid fractions in natural soils. Geoderma111(1-2), 75-84. https://doi.org/10.1016/S0016-7061(02)00254-9
Elgala, A. M., El‐Damaty, A. H., & Abdel‐Latif, I. (1976). Comparative ability of natural humus materials and synthetic chelates in extracting Fe, Mn, Zn, and Ca from soils. Zeitschrift für Pflanzenernährung und Bodenkunde139(3), 301-307. https://doi.org/10.1002/jpln.19761390305
Eshwar, M., Srilatha, M., Rekha, K. B., & Sharma, S. H. K. (2017). Complexation behavior of humic and fulvic acids with metal ions and their assessment by stability constants. International Journal of Pure & Applied Bioscience5(6), 899-907.
Gan, D., Kotob, S. I., & Walia, D. S. (2007). EVALUATION OF A SPECTROPHOTOMETRIC METHOD FOR PRACTICAL AND COST EFFECTIVE QUANTIFICATION OF FULVIC ACID. Annals of Environmental Science.
Güngör, E. B. Ö., & Bekbölet, M. (2010). Zinc release by humic and fulvic acid as influenced by pH, complexation and DOC sorption. Geoderma159(1-2), 131-138. https://doi.org/10.1016/j.geoderma.2010.07.004
Gupta, U. C., Kening, W. U., & Liang, S. (2008). Micronutrients in soils, crops, and livestock. Earth Science Frontiers15(5), 110-125. https://doi.org/10.1016/S1872-5791(09)60003-8
Harmsen, K., & Vlek, P. L. G. (1985). The chemistry of micronutrients in soil. In Micronutrients in tropical food crop production (pp. 1-42). Dordrecht: Springer Netherlands. https://doi.org/10.1007/978-94-009-5055-9_1
Hartz, T. K. (2007). Evaluation of humic substances used in commercial fertilizer formulation. Final Report, Frep Project, 07-0174.
Janoš, P., Vávrová, J., Herzogová, L., & Pilařová, V. (2010). Effects of inorganic and organic amendments on the mobility (leachability) of heavy metals in contaminated soil: a sequential extraction study. Geoderma159(3-4), 335-341. https://doi.org/10.1016/j.geoderma.2010.08.009
Keiluweit, M., Nico, P., Harmon, M. E., Mao, J., Pett-Ridge, J., & Kleber, M. (2015). Long-term litter decomposition controlled by manganese redox cycling. Proceedings of the National Academy of Sciences112(38), E5253-E5260. https://doi.org/10.1073/pnas.1508945112
Khattak, R. A., & Page, A. L. (2017). Mechanism of manganese adsorption on soil constituents. In Biogeochemistry of trace metals (pp. 395-412). CRC Press.
Khoshru, B., Mitra, D., Nosratabad, A. F., Reyhanitabar, A., Mandal, L., Farda, B., ... & Mohapatra, P. K. D. (2023). Enhancing manganese availability for plants through microbial potential: A sustainable approach for improving soil health and food security. Bacteria2(3), 129-141. https://doi.org/10.3390/bacteria2030010
Kumar, D., Patel, K. P., Ramani, V. P., Shukla, A. K., & Meena, R. S. (2020). Management of micronutrients in soil for the nutritional security. Nutrient Dynamics for Sustainable Crop Production, 103-134. https://doi.org/10.1007/978-981-13-8660-2_4
Lamar, R. T., & Monda, H. (2022). Quantification of Humic and Fulvic Acids in Humate Ores, DOC, Humified Materials and Humic Substance-Containing Commercial Products. JoVE (Journal of Visualized Experiments), (181), e61233. https://doi.org/10.3791/61233
Li, K., Shahab, A., Li, J., Huang, H., Sun, X., You, S., ... & Xiao, H. (2023). Compost-derived humic and fulvic acid coupling with Shewanella oneidensis MR-1 for the bioreduction of Cr (VI). Journal of Environmental Management, 345, 118596. https://doi.org/10.1016/j.jenvman.2023.118596
Li, H., Santos, F., Butler, K., & Herndon, E. (2021). A critical review on the multiple roles of manganese in stabilizing and destabilizing soil organic matter. Environmental science & technology55(18), 12136-12152. https://doi.org/10.1021/acs.est.1c00299
Mohiuddin, M., Irshad, M., Sher, S., Hayat, F., Ashraf, A., Masood, S., ... & Waseem, M. (2022). Relationship of selected soil properties with the micronutrients in salt-affected soils. Land, 11(6), 845.  https://doi.org/10.3390/land11060845
Muscolo, A., Sidari, M., & Nardi, S. (2013). Humic substance: relationship between structure and activity. Deeper information suggests univocal findings. Journal of Geochemical Exploration129, 57-63. https://doi.org/10.1016/j.gexplo.2012.10.012
Nardi, S., Schiavon, M., & Francioso, O. (2021). Chemical structure and biological activity of humic substances define their role as plant growth promoters. Molecules26(8), 2256. https://doi.org/10.3390/molecules26082256
Paulus, E. L., & Vitousek, P. M. (2024). Manganese and soil organic carbon stability on a Hawaiian grassland rainfall gradient. Soil Biology and Biochemistry, 109418. https://doi.org/10.1016/j.soilbio.2024.109418
Rashid, M. A., & King, L. H. (1970). Major oxygen-containing functional groups present in humic and fulvic acid fractions isolated from contrasting marine environments. Geochimica et Cosmochimica Acta34(2), 193-201. https://doi.org/10.1016/0016-7037(70)90006-2
Rodríguez, F. J., & Núñez, L. A. (2011). Characterization of aquatic humic substances. Water and Environment Journal25(2), 163-170. ­https://doi.org/10.1111/j.1747-6593.2009.00205.x
Rutkowska, B., Szulc, W., Sosulski, T., & Stępień, W. (2014). Soil micronutrient availability to crops affected by long-term inorganic and organic fertilizer applications.
Sarlaki, E., Paghaleh, A. S., Kianmehr, M. H., & Vakilian, K. A. (2020). Chemical, spectral and morphological characterization of humic acids extracted and membrane purified from lignite. Chem. Chem. Technol14(3), 353-361. https://doi.org/10.23939/chcht14.03.353
Senesi, N., D'Orazio, V., & Ricca, G. (2003). Humic acids in the first generation of EUROSOILS. Geoderma116(3-4), 325-344.­ https://doi.org/10.1016/S0016-7061(03)00107-1
Shakeri, S., & Saffari, M. (2020). The status of chemical forms of iron and manganese in various orders of calcareous soils and their relationship with some physicochemical and mineralogical properties. Communications in Soil Science and Plant Analysis, 51(15), 2054-2068. https://doi.org/10.1080/00103624.2020.1820026
Shuzhuan, W. A. N. G., Xiaorong, W. E. I., & Mingde, H. A. O. (2016). Dynamics and availability of different pools of manganese in semiarid soils as affected by cropping system and fertilization. Pedosphere26(3), 351-361. https://doi.org/10.1016/S1002-0160(15)60048-0
Singh, M., Sarkar, B., Hussain, S., Ok, Y. S., Bolan, N. S., & Churchman, G. J. (2017). Influence of physico-chemical properties of soil clay fractions on the retention of dissolved organic carbon. Environmental geochemistry and health39, 1335-1350.
https://doi.org/10.1007/s10653-017-9939-0
Sparks, D. L. (1996). Methods of soil analysis, part 3. Published by the chemical methods. Soil Science Society of America. Inc, Madison. Sparks, D. L. (1996). Methods of soil analysis, part 3. Published by the chemical methods. Soil Science Society of America. Inc, Madison.
Sparks, D. L., Singh, B., & Siebecker, M. G. (2022). Environmental soil chemistry. Elsevier.
Sposito, G. (2016). The chemistry of soils. Oxford university press.
Stevenson, F. J. (1991). Organic matter‐micronutrient reactions in soil. Micronutrients in agriculture4, 145-186. https://doi.org/10.2136/sssabookser4.2ed.c6
Swift, R. S. (1996). Organic matter characterization. Methods of soil analysis: Part 3 chemical methods5, 1011-1069. https://doi.org/10.2136/sssabookser5.3.c35
Türkmen, C., & Sungur, A. (2014). Influence of humic acid on availability of zn, Cu, mn, fe in soils. Asian Journal of Chemistry26(13), 3977.
Ussiri, D. A., & Johnson, C. E. (2003). Characterization of organic matter in a northern hardwood forest soil by 13C NMR spectroscopy and chemical methods. Geoderma111(1-2), 123-149. https://doi.org/10.1016/S0016-7061(02)00257-4
Verrillo, M., Salzano, M., Savy, D., Di Meo, V., Valentini, M., Cozzolino, V., & Piccolo, A. (2022). Antibacterial and antioxidant properties of humic substances from composted agricultural biomasses. Chemical and Biological Technologies in Agriculture9(1), 28. https://doi.org/10.1186/s40538-022-00291-6
Wandansari, N. R., Suntari, R., & Kurniawan, S. (2023). The role of humic acid from various composts in improving degraded soil fertility and maize yield. Journal of Degraded & Mining Lands Management10(2). https://doi.org/10.15243/jdmlm.2023.102.4245
Wang, M., Zhao, Z., Li, Y., Liang, S., Meng, Y., Ren, T., ... & Zhang, Y. (2022). Control the greenhouse gas emission via mediating the dissimilatory iron reduction: Fulvic acid inhibit secondary mineralization of ferrihydrite. Water Research, 218, 118501. https://doi.org/10.1016/j.watres.2022.118501
Wang, X., Wang, Q., Zhang, D., Liu, J., Fang, W., Li, Y., ... & Yan, D. (2024). Fumigation alters the manganese-oxidizing microbial communities to enhance soil manganese availability and increase tomato yield. Science of The Total Environment, 170882. https://doi.org/10.1016/j.scitotenv.2024.170882
Welch, R. M., & Graham, R. D. (2005). Agriculture: the real nexus for enhancing bioavailable micronutrients in food crops. Journal of Trace Elements in Medicine and Biology18(4), 299-307. https://doi.org/10.1016/j.jtemb.2005.03.001
Whalen, E. D., Smith, R. G., Grandy, A. S., & Frey, S. D. (2018). Manganese limitation as a mechanism for reduced decomposition in soils under atmospheric nitrogen deposition. Soil Biology and Biochemistry127, 252-263. https://doi.org/10.1016/j.soilbio.2018.09.025
Wu, J., West, L. J., & Stewart, D. I. (2002). Effect of humic substances on Cu (II) solubility in kaolin-sand soil. Journal of Hazardous Materials, 94(3), 223-238. https://doi.org/10.1016/S0304-3894(02)00082-1
Zanin, L., Tomasi, N., Cesco, S., Varanini, Z., & Pinton, R. (2019). Humic substances contribute to plant iron nutrition acting as chelators and biostimulants. Frontiers in Plant Science10, 452874. https://doi.org/10.3389/fpls.2019.00675