Abstract
Purpose
Structural studies on fulvic acids (FAs) are of significant importance since FAs are involved in many environmentally important processes, such as adsorption and transportation of nutrients, trace elements, and organic pollutants. Interactions between suspended and dissolved soil components are controlled by a variety of attractive and repulsive interparticle forces influenced partially by FA properties. The aim of this paper is a detailed characterization of FAs derived from agricultural soils varied with physicochemical properties.
Materials and methods
Forty topsoils (pHKCL = 3.8–7.8, clay content = 0–6%, and TOC = 7.0–187.2 g kg−1) were collected from rural area. Fulvic acids (FAs) were isolated according to the IHSS method. The overall FA solutions were purified by nonionic macroporous acrylic ester resin (DAX-8), and the organic carbon content in FA fraction (FA-OC) was determined by a liquid C–N analyzer. The particle size diameter (PSD) and polydispersity (PDI) were analyzed by a dynamic light scattering technique, while the zeta potential (ZP) was measured using an electrophoretic light scattering method. Spectroscopic properties of FAs, including occurrence and distribution of functional groups, were investigated by near-IR spectroscopy.
Results and discussion
Agricultural soils differed substantially, with FA-OC content ranging from 0.6 to 8.8 g kg−1 that accounted for 0.5 to 22.6% of TOC. The PSD exhibited wide range of particle size (0.2 to 69.6 nm) and was characterized by different polydispersity (14–183.1%). The ZP described the behavior, and surface charge of FA particles varied from − 1.7 to + 3.3 mV. Low ZP characterized 77% of FAs and indicated the ease of aggregate formation and intermolecular connections. The measured ZP also showed that suspended organic particles of FAs had both positive and negative charges, which was confirmed by the spectroscopic analysis. The presence of negative charges on FA particle surfaces was connected with the occurrence of phenol and carboxyl groups while positive charge with amine.
Conclusions
Detailed characterization of FAs from agricultural soils confirms their heterogeneous and complex nature. The results indicate that FAs mainly exist as small molecules that form molecular aggregates or associations in solutions. FA in a solution of a similar ionic strength may be positively or negatively charged due to its chemical structure and aggregate behavior which affects their properties in the soil.
Similar content being viewed by others
References
Alvarez-Puebla RA, Garrido J (2005) Effect of pH on the aggregation of a gray humic acid in colloidal and solid states. Chemosphere 59:659–667
Angelico R, Ceglie A, He J, Liu Y, Palumbo G, Colombo C (2014) Particle size, charge and colloidal stability of humic acids coprecipitated with ferrihydrite. Chemosphere 99:239–247
Anielak A, Grzegorczuk-Nowacka M (2011) Significance of zeta potential in the adsorption of fulvic acid on aluminum oxide and activated carbon. Pol J Environ Stud 20:1381–1386
Baldock J, Nelson P (2000) Soil organic matter. Handbook of soil science. Taylor and Francis Group, Boca Raton, pp 25–72
Brady NC (1990) The nature and properties of soils, 10th edn. Macmillan Publishing Co., New York, p 621
Chang RR, Mylotte R, Hayes MHB, McInerney R, Tzou YM (2014) A comparison of the compositional differences between humic fractions isolated by the IHSS and exhaustive extraction procedures. Naturwissenschaften 101:197–209
Chen Y, Schnitzer M (1976) Scanning electron microscopy of a humic acid and its metal and clay complexes. Soil Sci Soc Am J 40:682–686
Chin W-C, Orellana MC, Verdugo P (1998) Spontaneous assembly of marine dissolved organic matter into polymer gels. Nature 391:568–572
Debska B, Drag M, Banach-Szott M (2007) Molecular size distribution and hydrophilic and hydrophobic properties of humic acids isolated from forest soil. Soil. Water Res 2:45–53
Dick D, Santos J, Ferranti E (2003) Chemical characterization and infrared spectroscopy of soil organic matter from two southern Brazilian soils. Rev Bras Ciênc Solo 27:29–39
Donisa C, Mocanu R, Steinnes E (2003) Distribution of some major and minor elements between fulvic and humic acid fractions in natural soils. Geoderma 111:75–84
Esfahani M, Stretz HA, Wells MJM (2015) Abiotic reversible self-assembly of fulvic and humic acid aggregates in low electrolytic conductivity solutions by dynamic light scattering and zeta potential investigation. Sci Total Environ 537:81–92
Fuentes M, Baigorri B, González-Gaitano G, García-Mina J (2018) New methodology to assess the quantity and quality of humic substances in organic materials and commercial products for agriculture. J Soils Sediments 18:1389–1399
Gao Y, Yan M, Korshin GV (2015) Effects of ionic strength on the chromophores of dissolved organic matter. Environ Sci Technol 49:5905–5912
Gardiner DT, Miller RW (2004) Soils in our environment, 10th edn. Prentice-Hall, Inc., Upper Saddle River
Gessa C, Cessa C, Cabras MA, Micera G, Polemio M, Testini C (1983) Spectroscopic characterization of extracts from humic and fulvic fractions: IR and 1H NMR spectra. Plant Soil 75(2):169–177
Giesy JP, Alberts JJ, Evans DW (2010) Conditional stability constants and binding capacities for copper (II) by dissolved organic carbon isolated from surface waters of the southeastern United States. Environ Toxicol Chem 5:139–154
Gosh K, Mukherjee W (1971) Hymatomelanic acids as polyelectrolytes: I Viscosimetry and osmometric studies. J Appl Polym Sci 15:2073–2077
Griffith SM, Schnitzer M (1975) Analytical characteristics of humic and fulvic acids extracted from tropical volcanic soils. Soil Sci Soc Am J 39(5):861–867
Guo XJ, Zhu NM, Chen L, Yuan DH, He LS (2015) Characterizing the fluorescent properties and copper complexation of dissolved organic matter in saline-alkali soils using fluorescence excitation-emission matrix and parallel factor analysis. J Soils Sediments 15:1473–1482
Gustafsson JP, Persson I, Kleja DB, van Schaik JWJ (2007) Binding of iron(III) to organic soils: EXAFS spectroscopy and chemical equilibrium modeling. Environ Sci Technol 41:1232–1237
Hayes MBH (1985) Extraction of humic substances from soil. In: Aiken GR, McKnight DM, Wershaw RL, MacCarthy P (eds) Humic substances in soil, sediment, and water. Geochemistry, isolation, and characterization. Wiley-Interscience, New York, pp 329–362
Hunter R (1988) Zeta potential in colloidal science. In: Ottewill RH, Rowell RL (eds) Principles and applications. Academic Press Harcourt Brace Jovanovich, London
Jovanovic U, Markovic M, Cupac S, Tomic Z (2013) Soil humic acid aggregation by dynamic light scattering and laser Doppler electrophoresis. J Plant Nutr Soil Sci 176:674–679
Kawahigashi M, Sumida H, Yamamoto K (2005) Size and shape of soil humic acids estimated by viscosity and molecular weight. J Colloid Interface Sci 284:463–469
Klucakova M, Kalina M (2015) Composition, particle size, charge, and colloidal stability of pH-fractionated humic acids. J Soils Sediments 15:1900–1908
Mukherjee PN, Lahiri A (1959) Polyelectric behavior of humic acids. Fuel 37:220–226
Muller F (1996) Measurement of electrokinetic and size characteristics of estuarine colloids by dynamic light scattering spectroscopy. Anal Chim Act 331:1–15
Myneni SCB, Brown JT, Martinez GA, Meyer-Ilse W (1999) Imaging of humic substance macromolecular structures in water and soils. Science 286:1335–1337
Oriekhova O, Stoll S (2016) Effects of pH and fulvic acids concentration on the stability of fulvic acids—cerium (IV) oxide nanoparticle complexes. Chemosphere 144:131–137
Orlov DS (1985) Humus acids of soils. Moscow University Press, Amerind Publ, New Delhi
Pace ML, Reche I, Cole JJ, Fernández-Barbero A, Mazuecos IP, Prairie YT (2012) pH change induces shifts in the size and light absorption of dissolved organic matter. Biogeochemistry 108:109–118
Piccolo A (2001) The supramolecular structure of humic substances. Soil Sci 166:810–832
Piccolo A, Conte P, Cozzolino A (1999) Effects of mineral and monocarboxylic acids on the molecular association of dissolved humic substances. Eur J Soil Sci 50:687–694
Plaza C, Brunetti G, Senesi N, Polo A (2006) Molecular and quantitative analysis of metal ion binding to humic acids from sewage sludge and sludge-amended soils by fluorescence spectroscopy. Environ Sci Technol 40:917–923
Romera-Castillo C, Chen M, Yamashita Y, Jaffé R (2014) Fluorescence characteristics of size-fractionated dissolved organic matter: implications for a molecular assembly based structure? Water Res 55:40–51
Santschi PH, Balnois E, Wilkinson K, Zhang J, Buffle J, Guo L (1998) Fibrillar polysaccharides in marine macromolecular organic matter, as imaged by atomic force microscopy and transmission electron microscopy. Limnol Oceanogr 43:896–908
Schaumann GE (2006a) Soil organic matter beyond molecular structure part I: macromolecular and supramolecular characteristics. J Soil Sci Plant Nutr 169:145–156
Schaumann GE (2006b) Soil organic matter beyond molecular structure part II: amorphous nature and physical aging. J Soil Sci Plant Nutr 169:157–167
Schnitzer M (1976) Recent findings on the characterization of humic substances extracted from soils from widely different climate zones. Proc. of Symp. on Soil Organic Matter Studies, Braunschweig, pp 117–132
Schnitzer M (1978) Humic substances: chemistry and reactions. In: Schnitzer M, Khan SU (eds) Soil Organic Matter. Elsevier, Amsterdam, pp 1–64
Schnitzer M, Monreal CM (2011) Quo vadis soil organic matter research? A biological link to the chemistry of humification. In: Sparks DL (ed) Advances in agronomy 113. Elsevier Academic Press Inc, San Diego, pp 139–213
Schnitzer M, Skinner S (1968) Alkali versus acid extraction or soil organic matter. Soil Sci 105:392–396
Senesi N (1990) Molecular and quantitative aspects of the chemistry of fulvic acid and its interactions with metal ions and organic chemicals: Part I The electron spin resonance approach. Anal Chim Acta 232:51–75
Senesi N, Miano T, Provenzano M, Brunetti G (1991) Characterization, differentiation, and classification of humic substances by fluorescence spectroscopy. Soil Sci 152:4
Siéliéchi JM, Lartiges BS, Kayem GJ, Hupont S, Frochot C, Thieme J, Ghanbaja J, d’Espinose de la Caillerie JB, Barrès O, Kamga R, Levitz P, Michot LJ (2008) Changes in humic acid conformation during coagulation with ferric chloride: implications for drinking water treatment. Water Res 42:2111–2123
Steelink (1985) Implications of elemental characteristics of humic substances. In: Aiken GR, McKnight DM, Wershaw RL, MacCarthy P (eds) Humic Substances in Soil, Sediment, and Water. Geochemistry, Isolation and Characterization. Wiley, New York, pp 457–476
Steinberg C (2003) Ecology of humic substances in freshwaters: determinants from geochemistry to ecological niches. Springer, Berlin and New York
Stevenson FJ (1976) Stability constants of Cu2+, Pb2+ and Cd2+ complexes with humic acids. Soil Sci Am J 40:665–672
Stevenson (1977) Nature of divalent transition metal complexes of humic acids as revealed by modified titration method. Soil Sci 123:10–17
Stevenson FJ (1982) Humus chemistry, genesis, compositions, reactions. Wiley, New York
Swift RS (1985) Fractionation of soil humic substances. In: Aiken G, McKnight DM, Wershaw RL, MacCarthy P (eds) Humc substances in soil, sediment and water. Willey, New York, pp 387–408
Tan KH (1985) Scanning electron microscopy of humic matter as influenced by methods of preparation. Soil Sci Soc Am J 49:1185–1191
Tan KH (2014) Humic matter in soil and the environment: principles and controversies. CRC Press, Boca Raton ISBN 978-1-4822-3445-9
Timko SA, Gonsior M, Cooper WJ (2015) Influence of pH on fluorescent dissolved organic matter photo-degradation. Water Res 85:266–274
Tinoco P, Almendros G, González-Vila F, Sanz J, González-Pérez J (2015) Revisiting molecular characteristics responsive for the aromaticity of soil humic acids. J Soils Sediments 15:781–791
Visser SA (1964) Physico-chemical of the properties of humic acids and their charges during humification. J Soil Sci 15:202–219
Watanabe A, Rumbanraja J, Tsutsuki K, Kimura M (2001) Humus composition of soils under forest, coffee and arable cultivation in hilly areas of South Sumatra, Indonesia. Eur J Soil Sci 52:599–606
Xu J, Zhao B, Chu W, Mao J, Zhang J (2017) Chemical nature of humic substances in two typical Chinese soils (upland vs paddy soil): a comparative advanced solid state NMR study. Sci Total Environ 576:444–452
Yamashita Y, Jaffe R (2008) Characterizing the interactions between trace metals and dissolved organic matter using excitation emission matrix and parallel factor analysis. Environ Sci Technol 42:7374–7379
Yan M, Fu Q, Li D, Gao G, Wang D (2013) Study of the pH influence on the optical properties of dissolved organic matter using fluorescence excitation-emission matrix and parallel factor analysis. J Lumin 142:103–109
Yu J, Xu Q, Liu Z, Guo X, Han S, Yuan S, Tong L (2013) Morphological characteristics of fulvic acid fractions observed by atomic force microscopy. J Mic 252:71–78
Acknowledgements
The financial support from the National Science Centre grant no. UMO-2011/03/B/ST10/05015 and no. UMO-2012/07/B/ST10/04387 is kindly acknowledged. The research was also partially financed by Ministry of Agriculture and Rural Development (PL) State Programme, Task 1.3 (2016-2020). We also gratefully acknowledge the Anton Paar Poland sp. z oo.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Claudio Bini
Rights and permissions
About this article
Cite this article
Ukalska-Jaruga, A., Debaene, G. & Smreczak, B. Particle and structure characterization of fulvic acids from agricultural soils. J Soils Sediments 18, 2833–2843 (2018). https://doi.org/10.1007/s11368-018-2008-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11368-018-2008-1