Changes in Molecular Structure of Humic Substances in Cambisols under Agricultural Use
Abstract
:1. Introduction
2. Materials and Methods
3. Results and Discussion
3.1. SOC Content
3.2. Elemental Analysis
3.3. Humic Acids’ Molecular Structure (by Means of 13C NMR Spectroscopy)
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
- West, T.O.; Post, W.M. Soil organic carbon sequestration rates by tillage and crop rotation: A Global Data Analysis. Soil Sci. Soc. Am. J. 2002, 66, 1930–1946. [Google Scholar] [CrossRef]
- Yu, B.; Stott, P.; Di, X.Y.; Yu, H.X. Assessment of land cover changes and their effect on soil organic carbon and soil total nitrogen in Daqing Prefecture, China. Land Degrad. Dev. 2014, 25, 520–531. [Google Scholar] [CrossRef]
- He, C.; Chen, Z.; Qiu, K.-Y.; Chen, J.-S.; Bohoussou, Y.N.; Dang, Y.P.; Zhang, H.-L. Effects of conservation agriculture on carbon mineralization: A global meta-analysis. Soil Till. Res. 2023, 229, 105685. [Google Scholar] [CrossRef]
- Orlov, D.S. Humic Substances of Soils and General Theory of Humification, 1st ed.; Taylor & Francis: London, UK, 1995; 325p. [Google Scholar] [CrossRef]
- Guo, X.; Liu, H.; Wu, S. Humic substances developed during organic waste composting: Formation mechanisms, structural properties, and agronomic functions. Sci. Total Environ. 2019, 662, 501–510. [Google Scholar] [CrossRef]
- Piccolo, A.; Spaccini, R.; Drosos, M.; Vinci, G.; Cozzolino, V. The Molecular Composition of Humus Carbon: Recalcitrance and Reactivity in Soils. In The Future of Soil Carbon; Garcia, C., Nannipieri, P., Hernandez, T., Eds.; Academic Press: Cambridge, MA, USA, 2018; pp. 87–124. [Google Scholar]
- Hoffland, E.; Kuyper, T.W.; Comans, R.N.J.; Creamer, R.E. Eco-functionality of organic matter in soils. Plant Soil 2020, 455, 1–22. [Google Scholar] [CrossRef]
- Chukov, S.N. Structural and Functional Parameters of Soil Organic Matter under Anthropogenic Impact; Publishing House of St. Petersburg University: St. Petersburg, Russia, 2001. [Google Scholar]
- Plante, A.F.; Fernández, J.M.; Haddix, M.L.; Steinweg, J.M.; Conant, R.T. Biological, chemical and thermal indices of soil organic matter stability in four grassland soils. Soil Biol. Biochem. 2011, 43, 1051–1058. [Google Scholar] [CrossRef]
- Gregorich, E.G.; Gillespie, A.W.; Beare, M.H.; Curtin, D.; Sanei, H.; Yanni, S.F. Evaluating biodegradability of soil organic matter by its thermal stability and chemical composition. Soil Biol. Biochem. 2015, 91, 182–191. [Google Scholar] [CrossRef]
- Dou, S.; Tardy, Y.; Zhang, J.; Li, K. The thermodynamics stability of soil humic and fulvic acids. In Proceedings of the 19th World Congress of Soil Science: Soil Solutions for a Changing World, Brisbane, Australia, 1–6 August 2010. [Google Scholar]
- Zalidis, G.; Stamatiadis, I.; Takavakoglou, V.; Eskridge, K.; Misopolinos, N. Impacts of agricultural practices on soil and water quality in the Mediterranean region and proposed assessment methodology. Agric. Ecosyst. Environ. 2002, 88, 137–146. [Google Scholar] [CrossRef]
- Pare, T.; Dinel, H.; Moulin, A.P.; Townley-Smith, L. Organic matter quality and structural stability of a black chernozemic soil under different manure and tillage practices. Geoderma 1999, 91, 311–326. [Google Scholar] [CrossRef]
- Buurman, P.; Roscoe, R. Different chemical composition of free light, occluded light, and extractable SOM fractions in soils of Cerrado and tilled and untilled fields, Minas Gerais, Brazil: A pyrolysis-GC/MS study. Eurasian Soil Sci. 2011, 62, 253–266. [Google Scholar] [CrossRef]
- Chan, K.Y.; Heenan, D.P.; Oates, A. Soil carbon fractions and relationship to soil quality under different tillage and stubble management. Soil Till Res. 2002, 63, 133–139. [Google Scholar] [CrossRef]
- Ghani, A.; Dexter, M.; Perrott, K.W. Hot-water extractable carbon in soils: A sensitive measurement for determining impacts of fertilization, grazing and cultivation. Soil Biol. Biochem. 2003, 35, 1231–1243. [Google Scholar] [CrossRef]
- Lodygin, E.; Abakumov, E. The Impact of Agricultural Use of Retisols on the Molecular Structure of Humic Substances. Agronomy 2022, 12, 144. [Google Scholar] [CrossRef]
- Zhang, J.; Wang, J.; An, T.; Wey, D.; Chi, F.; Zhou, B. Effects of long-term fertilizationon soil humuic acid composition and structure in Black Soil. PLoS ONE 2017, 12, 0186918. [Google Scholar] [CrossRef]
- De Mastro, F.; Cocozza, C.; Traversa, A.; Savy, D.; Abdelrahman, H.M.; Brunetti, G. Influence of crop rotation, tillage and fertilization on chemical and spectroscopic characteristic of humic acids. PLoS ONE 2019, 14, 0219099. [Google Scholar] [CrossRef] [PubMed]
- Preston, C.M. Applications of NMR to soil organic matter analysis: History and prospects. Soil Sci. 1996, 161, 144–166. [Google Scholar] [CrossRef]
- Kovalevskii, D.V.; Permin, A.B.; Perminova, I.V.; Petrosyan, V.S. Conditions for acquiring quantitative 13C NMR spectra of humic substances. Mosc. Univ. Chem. Bull. 2000, 41, 39–42. [Google Scholar]
- Cao, X.Y.; Olk, D.C.; Chappell, M.; Cambardella, C.A.; Miller, L.F.; Mao, J. Solid-state NMR analysis of soil organic matter fractions from integrated physical-chemical extraction. Soil Sci. Soc. Am. J. 2011, 75, 1374–1384. [Google Scholar] [CrossRef]
- Kholodov, V.A.; Konstantinov, A.I.; Kudryavtsev, A.V.; Perminova, I.V. Structure of humic acids in zonal soils from 13C NMR data. Eurasian Soil Sci. 2011, 44, 976–983. [Google Scholar] [CrossRef]
- IUSS Working Group WRB. International Union of Soil Sciences (IUSS), Vienna, Austria. 2022. Available online: https://wrb.isric.org/files/WRB_fourth_edition_2022-12-18.pdf (accessed on 28 August 2023).
- Badmaev, N.; Bazarov, A. Monitoring Network for Atmospheric and Soil Parameters Measurements in Permafrost Area of Buryatia, Russian Federation. Geosciences 2019, 9, 6. [Google Scholar] [CrossRef]
- Kulikov, A.I.; Ubugunov, L.L.; Mangataev, A.T. On global climate change and its ecosystem consequences. Arid Ecosyst. 2014, 4, 135–141. [Google Scholar] [CrossRef]
- Soil Survey Staff. Soil Survey Laboratory Methods Manual; Soil Survey Investigations Report No 42; USDA—NRCS: Washington, DC, USA, 2004.
- ISO 10694:1995; Soil Quality—Determination of Organic and Total Carbon after Dry Combustion (Elementary Analysis). ISO: Geneva, Switzerland, 1995.
- Kalabin, G.A.; Kanitskaya, L.V.; Kushnarev, D.V. Quantitative NMR Spectroscopy of Natural Organic Raw Materials and Products of Its Processing; Chemistry: Moscow, Russia, 2000. [Google Scholar]
- Hertkorn, N.; Permin, A.B.; Perminova, I.V.; Kovalevskii, D.V.; Yudov, M.V.; Kettrup, A. Comparative analysis of partial structures of a peat humic and fulvic acid using one and two dimensional nuclear magnetic resonance spectroscopy. J. Environ. Qual. 2002, 31, 375–387. [Google Scholar] [CrossRef]
- Kuznetsova, I.V. Changes in the physical status of the typical and leached chernozems of Kursk oblast within 40 years. Eurasian Soil Sci. 2013, 46, 393–400. [Google Scholar] [CrossRef]
- Vishnyakova, O.V.; Chimitdorzhieva, G.D. Humic acids in meadow-chernozemic permafrost-affected soils of the Transbaikal Region. Eurasian Soil Sci. 2008, 41, 704–707. [Google Scholar] [CrossRef]
- Vishnyakova, O.V.; Chimitdorzhieva, G.D.; Ayurova, D.B. Structural Changes in Humic Acids from Arable Chernozems and Meadow-chernozemic Cryogenic Soils of Transbaikalia. Agrochemistry 2011, 10, 3–8. [Google Scholar]
- Lodygin, E.; Beznosikov, V.; Abakumov, E. Humic substances elemental composition of selected taiga and tundra soils from Russian European North-East. Pol. Polar Res. 2017, 38, 125–147. [Google Scholar] [CrossRef]
- Dergacheva, M.I.; Nekrasova, O.A.; Okoneshnikova, M.V.; Vasil’eva, D.I.; Gavrilov, D.A.; Ochur, K.O.; Ondar, E.E. Ratio of Elements in humic acids as a source of information on the environment of soil formation. Contemp. Probl. Ecol. 2012, 5, 497–504. [Google Scholar] [CrossRef]
- Vasilevich, R.; Lodygin, E.; Abakumov, E. The Molecular Composition of Humic Acids in Permafrost Peats in the European Arctic as Paleorecord of the Environmental Conditions of the Holocene. Agronomy 2022, 12, 2053. [Google Scholar] [CrossRef]
- Kholodov, V.A.; Yaroslavtseva, N.V.; Farkhodov, Y.R.; Belobrov, V.P.; Yudin, S.A.; Frid, A.S.; Aydiev, A.Y.; Lazarev, V.I. Changes in the ratio of aggregate fractions in humus horizons of chernozems in response to the type of their use. Eurasian Soil Sci. 2019, 52, 162–170. [Google Scholar] [CrossRef]
- Ma, J.; Xiao, B. Review on extraction and fractionation of humic substances from soils. Bull. Mineral. Petrol. Geochemistry 2011, 30, 465–471. [Google Scholar]
- Piccolo, A.; Spaccini, R.; Savy, D.; Drosos, M.; Cozzolino, V. The soil Humeome: Chemical structure, functions and technological perspectives. In Sustainable Agrochemistry; Vaz, S., Jr., Ed.; Springer Nature: Cham, Switzerland, 2019; pp. 183–222. [Google Scholar] [CrossRef]
- Zavarzina, A.G.; Kravchenko, E.G.; Konstantinova, A.I.; Perminova, I.V.; Chukov, S.N.; Demin, V.V. Comparison of the properties of humic acids extracted from soils by alkali in the presence and absence of oxygen. Eurasian Soil Sci. 2019, 52, 880–891. [Google Scholar] [CrossRef]
- Kholodov, V.A.; Konstantinov, A.I.; Belyaeva, E.Y.; Kulikova, N.A.; Kiryushin, A.V.; Perminova, I.V. Structure of humic acids isolated by sequential alkaline extraction from a Typical Chernozem. Eurasian Soil Sci. 2009, 42, 1095–1100. [Google Scholar] [CrossRef]
- Ndzelu, B.S.; Dou, S.; Zhang, X.; Zhang, Y.; Ma, R.; Liu, X. Tillage Effects on humus composition and humic acid structural characteristics in soil aggregate-size fractions. Soil Till Res. 2021, 216, 105090. [Google Scholar] [CrossRef]
- Spaccini, R.; Piccolo, A. Effects of field managements for soil organic matter stabilization on water-stable aggregate distribution and aggregate stability in three agricultural soils. Geochem. Explor. 2013, 129, 45–51. [Google Scholar] [CrossRef]
- Fedorova, T.E.; Kushnarev, D.F.; Vashukevich, N.V.; Proidakov, A.G.; Byambagar, B.; Kalabin, G.A. 13C NMR Spectroscopy of humic acids of different origin. Eurasian Soil Sci. 2003, 36, 1080–1084. [Google Scholar]
- Tikhova, V.D.; Shakirov, M.M.; Fadeeva, V.P.; Dergacheva, M.I.; Samutenko, L.V.; Fedorova, L.V. NMR study of structural changes in humic acids of meadow soddy soils. Russ. J. Appl. Chem. 2002, 75, 829–833. [Google Scholar] [CrossRef]
- Chukov, S.N.; Lodygin, E.D.; Abakumov, E.V. Application of 13C NMR spectroscopy to the study of soil organic matter: A review of publications. Eurasian Soil Sci. 2018, 51, 889–900. [Google Scholar] [CrossRef]
- Baldock, J.A.; Preston, C.M. Chemistry of carbon decomposition processes in forests as revealed by solid-state carbon-13 nuclear magnetic resonance. In Carbon Forms and Functions in Forest Soils; Kelly, J.M., McFee, W.W., Eds.; Soil Science Society of America: Madison, WI, USA, 1995; pp. 89–117. [Google Scholar]
- Kholodov, V.A.; Yaroslavtseva, N.V.; Konstantinov, A.I.; Perminova, I.V. Preparative yield and properties of humic acids obtained by sequential alkaline extractions. Eurasian Soil Sci. 2015, 48, 1101–1109. [Google Scholar] [CrossRef]
- Savarese, C.; Drosos, M.; Spaccini, R.; Cozzolino, V.; Piccolo, A. Molecular characterization of soil organic matter and its extractable humic fraction from long-term field experiments under different cropping systems. Geoderma 2020, 383, 114700. [Google Scholar] [CrossRef]
Horizon | Depth | pHH2O | Organic Carbon, % | Total Nitrogen, % | P2O5, mg/100 g | Texture Fractions, % | ||
---|---|---|---|---|---|---|---|---|
2–0.05 | 0.05–0.002 | <0.002 | ||||||
mm | ||||||||
Eutric Cambisol Cryic (Gleyic, Humic, Loamic) | ||||||||
Ah | 5–25 | 7.1 ± 0.2 | 3.4 ± 0.3 | 0.91 ± 0.18 | 95.0 ± 17.2 | 60.5 ± 12.1 | 35.5 ± 7.1 | 4.0 ± 0.8 |
AhBwtu | 25–70 | 7.5 ± 0.2 | 1.5 ± 0.1 | 0.53 ± 0.11 | 55.0 ± 9.8 | 44.5 ± 8.9 | 37.3 ± 7.5 | 18.2 ± 3.6 |
Bccgl | 70–90 | 8.3 ± 0.2 | - | - | 45.6 ± 7.2 | 44.1 ± 8.8 | 30.4 ± 6.1 | 25.5 ± 5.1 |
Eutric Cambisol Cryic (Humic, Loamic) arable | ||||||||
Ap | 0–20 | 6.9 | 3.1 ± 0.3 | 0.62 ± 0.12 | 79.2 ± 12.2 | 55.0 ± 11.0 | 40.2 ± 8.0 | 4.8 ± 1.0 |
Bw | 20–65 | 7.5 | 0.9 ± 0.1 | 0.21 ± 0.04 | 48.3 ± 8.1 | 46.4 ± 9.3 | 41.4 ± 8.3 | 12.2 ± 2.4 |
BCcc | 65–95 | 7.9 | - | - | 37.5 ± 6.2 | 42.1 ± 8.4 | 36.5 ± 7.3 | 21.4 ± 4.3 |
Haplic Cambisol (Arenic, Humic, Protocalcic) | ||||||||
Ah | 5–25 | 6.9 ± 0.3 | 2.8 ± 0.2 | 0.23 ± 0.04 | 38.0 ± 6.3 | 65.1 ± 13.2 | 33.3 ± 6.6 | 1.6 ± 0.3 |
Bw | 25–65 | 7.6 ± 0.2 | 0.6 ± 0.05 | 0.06 ± 0.01 | 22.2 ± 3.7 | 54.5 ± 10.9 | 44.1 ± 8.8 | 1.4 ± 0.3 |
Bqc | 65–97 | 8.2 ± 0.3 | - | - | 12.1 ± 2.0 | 56.5 ± 11.1 | 37.8 ± 7.6 | 5.7 ± 1.1 |
Haplic Cambisol (Arenic, Humic, Protocalcic) arable | ||||||||
Ap | 0–20 | 7.1 ± 0.2 | 2.0 ± 0.2 | 0.12 ± 0.02 | 20.5 ± 4.2 | 68.2 ± 12.0 | 30.5 ± 7.7 | 1.3 ± 0.3 |
Bw | 20–60 | 7.6 ± 0.2 | 0.5 ± 0.04 | 0.05 ± 0.01 | 12.7 ± 3.0 | 55.3 ± 11.1 | 43.1 ± 8.6 | 1.6 ± 0.3 |
Bqc | 60–90 | 8.1 ± 0.2 | - | - | 7.2 ± 1.2 | 50.6 ± 10.1 | 44.5 ± 8.9 | 4.9 ± 1.0 |
Soil | The Content, Weight % Molar % | Atomic Ratios | H/Ccor 1 | Oxidation Rate (ϖ) 2 | |||||
---|---|---|---|---|---|---|---|---|---|
C | H | N | O | H/C | O/C | C/N | |||
EC 3 | 52.5 ± 0.5 39.0 ± 0.4 | 4.2 ± 0.2 37.0 ± 0.7 | 3.6 ± 0.1 2.0 ± 0.01 | 39.7 ± 0.4 22.0 ± 0.2 | 0.95 | 0.54 | 19.5 | 1.67 | +0.30 |
ECa | 51.5 ± 0.5 38.5 ± 0.4 | 4.1 ± 0.2 36.0 ± 0.6 | 2.8 ± 0.1 2.0 ± 0.01 | 41.6 ± 0.4 23.5 ± 0.2 | 0.94 | 0.61 | 19.0 | 1.77 | +0.44 |
HC | 48.4 ± 0.5 36.0 ± 0.3 | 4.4 ± 0.2 38.0 ± 0.8 | 3.3 ± 0.1 2.0 ± 0.01 | 43.9 ± 0.4 24.0 ± 0.2 | 1.06 | 0.67 | 18.0 | 1.95 | +0.44 |
HCa | 55.1 ± 0.6 40.0 ± 0.4 | 4.3 ± 0.2 37.0 ± 0.7 | 2.7 ± 0.1 2.0 ± 0.01 | 37.9 ± 0.4 21.0 ± 0.2 | 0.93 | 0.53 | 20.0 | 1.64 | +0.28 |
Chemical Shift, ppm | Structure Group |
---|---|
0–47 | Alkyl group C (–CH, –CH2, –CH3) |
47–60 | Amino group C and –O–CH3 structures |
60–108 | Carbohydrate, alcohol and ether –C–O groups |
108–164 | Aromatic Car, phenol CAr –O |
164–183 | Carboxyl C |
183–204 | Quinone CAr=O, aldehyde and ketone –C=O groups |
Plot N | Chemical Shift, ppm | ƩCar/ ƩCal | Aromaticity, % | |||||
---|---|---|---|---|---|---|---|---|
0–47 | 47–60 | 60–108 | 108–164 | 164–183 | 183–204 | |||
1 | 17.0 | 6.0 | 7.0 | 55.0 | 13.0 | 2.0 | 1.3 | 55.0 |
2 | 15.0 | 7.0 | 5.0 | 57.0 | 15.0 | 1.0 | 1.4 | 57.0 |
3 | 19.0 | 9.0 | 13.0 | 45.0 | 12.0 | 2.0 | 0.9 | 45.0 |
4 | 14.0 | 4.0 | 7.0 | 60.0 | 13.0 | 1.0 | 1.6 | 60.0 |
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Vishnyakova, O.; Ubugunov, L. Changes in Molecular Structure of Humic Substances in Cambisols under Agricultural Use. Agronomy 2023, 13, 2299. https://doi.org/10.3390/agronomy13092299
Vishnyakova O, Ubugunov L. Changes in Molecular Structure of Humic Substances in Cambisols under Agricultural Use. Agronomy. 2023; 13(9):2299. https://doi.org/10.3390/agronomy13092299
Chicago/Turabian StyleVishnyakova, Oksana, and Leonid Ubugunov. 2023. "Changes in Molecular Structure of Humic Substances in Cambisols under Agricultural Use" Agronomy 13, no. 9: 2299. https://doi.org/10.3390/agronomy13092299