Abstract
Purpose
Understanding the mechanisms of interaction between humic acids (HAs) and metal ions in soil media is essential for integrated environmental and agricultural management. This study aims to select the best isotherm model and explore the correlation between physicochemical properties of humic acids isolated from forest soils and metal ion sorption parameters.
Materials and methods
The HA fractions of ten forest soils were initially isolated and well characterized. Afterward, the sorption of four metal ions (Cu, Fe, Mn, and Zn) on the isolated HAs was investigated. The experimental data was initially fit to the three isotherm models to find the optimal model. Subsequently, the correlation between physicochemical HA properties and metal ion sorption parameters was explored using correlation and clustering analysis.
Results and discussion
Results showed that despite employing identical extraction procedures, isolated HAs from soils differed statistically in their descriptive characteristics. The adsorption data generally fit the Freundlich isotherm model best. However, isotherm model performance was affected by both metal ion and HA types. Six descriptive HA attributes including H/C and O/C molar ratio, the internal oxidation degree (ω), carboxylic acidity, E4/E6 ratio, and the Δlog-K were closely associated with sorption parameters.
Conclusions
Since the performance of isotherm models was affected by both metal ion and HA type, the isotherm model should be selected with regard to target metal ions and HA type. Highly correlated variables with sorption parameters of HA-metal ions screened in this study could be reliably used to develop sorption predictive models for HA-metal ions in soil and aquifers.
Graphical abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Availability of data and material
The electronic supplementary material can be seen in the Supplementary information of this article.
Abbreviations
- ANOVA:
-
Analysis of variance
- COOH:
-
Carboxylic acidity
- CV:
-
Coefficient of variation
- FA:
-
Fulvic acids
- HA:
-
Humic acid
- K1 :
-
Temkin isotherm constant relevant to the maximum binding energy
- K2 :
-
Temkin isotherm constant relevant to the heat of adsorption
- KF :
-
Freundlich isotherm constant relevant to adsorption capacity
- KL :
-
Langmuir equilibrium constant
- n:
-
A constant indicative of the intensity of adsorption in Freundlich isotherm model
- OH:
-
Phenolic acidity
- qm :
-
Langmuir monolayer sorption capacity
- r:
-
Pearson correlation coefficient
- R2 :
-
Coefficient of determination
- TA:
-
Total acidity
- η2 :
-
Partial eta squared
- κ:
-
Cohen’s kappa statistic
- ω:
-
Internal oxidation
References
Alkaram UF, Mukhlis AA, Al-Dujaili AH (2009) The removal of phenol from aqueous solutions by adsorption using surfactant-modified bentonite and kaolinite. J Hazard Mater 169:324–332. https://doi.org/10.1016/j.jhazmat.2009.03.153
Barančíková G, Makovníková J (2003) The influence of humic acid quality on the sorption and mobility of heavy metals. Plant Soil Environ 49:565–571. https://doi.org/10.17221/4195-PSE
Boguta P, D’Orazio V, Sokołowska Z, Senesi N (2016) Effects of selected chemical and physicochemical properties of humic acids from peat soils on their interaction mechanisms with copper ions at various pHs. J Geochem Explor 168:119–126. https://doi.org/10.1016/j.gexplo.2016.06.004
Boguta P, Sokołowska Z (2013) Interactions of humic acids with metals. Acta Agroph Monogr 2:1–113
Boguta P, Sokołowska Z (2014) Statistical relationship between selected physicochemical properties of peaty-muck soils and their fraction of humic acids. Int Agrophysics 28:269–278. https://doi.org/10.2478/intag-2014-0017
Boguta P, Sokołowska Z (2016) Interactions of Zn (II) Ions with humic acids isolated from various type of soils effect of pH, Zn concentrations and humic acids chemical properties. PLoS ONE 11:e0153626–e0153626. https://doi.org/10.1371/journal.pone.0153626
Carter MR, Gregorich EG (2008) Soil sampling and methods of analysis. CRC Press Lewis Publishers Boca Raton FL, Canadian Society of Soil Science
Chen J, Gu B, LeBoeuf EJ, Pan H, Dai S (2002) Spectroscopic characterization of the structural and functional properties of natural organic matter fractions. Chemosphere 48:59–68. https://doi.org/10.1016/S0045-6535(02)00041-3
Chianese S, Fenti A, Iovino P, Musmarra D, Salvestrini S (2020) Sorption of Organic Pollutants by Humic Acids: A Review. Molecules 25:918. https://doi.org/10.3390/molecules25040918
Cybulak M, Sokołowska Z, Boguta P (2021) The influence of biochar on the content of carbon and the chemical transformations of fallow and grassland humic acids. Sci Rep 11:5698. https://doi.org/10.1038/s41598-021-85239-w
Dauletbay A, Serikbayev BA, Kamysbayev DK, Kudreeva LK (2020) Interaction of metal ions with humic acids of brown coals of Kazakhstan. J Exp Nanosci 15:406–416. https://doi.org/10.1080/17458080.2020.1810240
Enev V, Pospíšilová L, Klučáková M, Liptaj T, Doskočil L (2014) Spectral characterization of selected humic substances. Soil Water Res 9:9–17. https://doi.org/10.17221/39/2013-SWR
Erdogan S, Baysal A, Akba O, Hamamci C (2007) Interaction of metals with humic acid isolated from oxidized coal. Pol J Environ Stud 16:671–675
Fernandes AN, Giovanela M, Esteves VI, Sierra MMdS (2010) Elemental and spectral properties of peat and soil samples and their respective humic substances. J Mol Struct 971:33–38. https://doi.org/10.1016/j.molstruc.2010.02.069
Förstner U, Wittmann GTW (2012) Metal pollution in the aquatic environment. Springer, Berlin Heidelberg
Giovanela M, Crespo J, Antunes M, Adametti DS, Fernandes A, Barison A, Silva C, Guegan R, Motelica-Heino M (2010) Chemical and spectroscopic characterization of humic acids extracted from the bottom sediments of a Brazilian subtropical microbasin. J Mol Struct 981:111–119. https://doi.org/10.1016/j.molstruc.2010.07.038
Helal AA, Murad GA, Helal AA (2011) Characterization of different humic materials by various analytical techniques. Arab J Chem 4:51–54. https://doi.org/10.1016/j.arabjc.2010.06.018
Irving H, Williams RJP (1948) Order of stability of metal complexes. Nature 162:746–747
Kelleher BP, Simpson AJ (2006) Humic substances in soils: are they really chemically distinct?. Environ Sci Technol 40:4605–4611. https://doi.org/10.1021/es0608085
Khalili F, Al-Banna G (2015) Adsorption of uranium(VI) and thorium(IV) by insolubilized humic acid from Ajloun soil–Jordan. J Environ Radioact 146:16–26. https://doi.org/10.1016/j.jenvrad.2015.03.035
Klučáková M, Pekař M (2006) New model for equilibrium sorption of metal ions on solid humic acids Colloids. Surf a: Physicochem Eng Asp 286:126–133. https://doi.org/10.1016/J.COLSURFA.2006.03.013
Kumar KV, Gadipelli S, Wood B, Ramisetty KA, Stewart AA, Howard CA, Brett DJL, Rodriguez-Reinoso F (2019) Characterization of adsorption site energies and heterogeneous surfaces of porous materials. J Mater Chem A. https://doi.org/10.1039/c9ta00287a
Martyniuk H, Więckowska J (2003) Adsorption of metal ions on humic acids extracted from brown coals Fuel Process. Technol 84:23–36. https://doi.org/10.1016/S0378-3820(02)00246-1
McHugh ML (2012) Interrater reliability: the kappa statistic. Biochem Med 22:276–282
Nagao S, Aramaki T, Fujitake N, Kodama H, Tanaka T, Ochiai S, Uchida M, Shibata Y, Yamamoto M (2013) Variation of Δ14C and δ13C values of dissolved humic and fulvic acids in the tokachi river system in Northern Japan. Radiocarbon 55:1007–1016. https://doi.org/10.1017/s0033822200058148
Olk DC, Bloom PR, Perdue EM, McKnight DM, Chen Y, Farenhorst A, Senesi N, Chin YP, Schmitt-Kopplin P, Hertkorn N, Harir M (2019) Environmental and agricultural relevance of humic fractions extracted by alkali from soils and natural waters. J Environ Qual 48:217–232. https://doi.org/10.2134/jeq2019.02.0041
Pandey AK, Pandey SD, Misra V (2000) Stability constants of metal-humic acid complexes and its role in environmental detoxification. Ecotoxicol Environ Saf 47:195–200. https://doi.org/10.1006/eesa.2000.1947
Peña-Méndez E, Havel J, Patocka J (2004) Humic substances-compounds of still unknown structure: applications in agriculture, industry, environment, and biomedicine. J Appl Biomed 3:13–24. https://doi.org/10.32725/jab.2005.002
Pereira JC, Bellato RC, Jham CR, Newandram G, Luis J (2001) Adsorption of Cu2+ ions on humic acids. Rev Esc De Minas 54:109–114. https://doi.org/10.1590/S0370-44672001000200006
Pérez-Esteban J, Escolástico C, Sanchis I, Masaguer A, Moliner A (2019) Effects of pH conditions and application rates of commercial humic substances on Cu and Zn mobility in anthropogenic mine soils. Sustainability 11:4844. https://doi.org/10.3390/su11184844
Piccolo A (2002) The supramolecular structure of humic substances: A novel understanding of humus chemistry and implications in soil science, Advances in Agronomy. Academic Press, pp 57–134. https://doi.org/10.1016/S0065-2113(02)75003-7
Piri M, Sepehr E, Rengel Z (2019) Citric acid decreased and humic acid increased Zn sorption in soils. Geoderma 341:39–45. https://doi.org/10.1016/j.geoderma.2018.12.027
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. https://doi.org/10.1021/es051687w
Purmalis O, Klavins M (2012) Formation and changes of humic acid properties during peat humification process within ombrotrophic bogs. Open J. Soil Sci. 2:100–110. https://doi.org/10.4236/ojss.2012.22015
Reddy SB, Nagaraja M, Punith T, Patil A, Dhumgond P (2014) Elemental analysis, e4/e6 ratio and total acidity of soil humic and fulvic acids from different land use systems. Ann Plant Soil Res 16:89–92
Rodríguez FJ, Nunez LA (2011) Characterization of aquatic humic substances. Water Environ J 25:163–170. https://doi.org/10.1111/j.1747-6593.2009.00205.x
Santos Ad, Botero WG, Bellin IC, Oliveira LCd, Rocha JC, Mendonça AGR, Godinho AF (2007) Interaction between humic substances and metallic ions: a selectivity study of humic substances and their possible therapeutic application. J Braz Chem Soc 18:824–830. https://doi.org/10.1590/S0103-50532007000400023
Shi W, Lü C, He J, En H, Gao M, Zhao B, Zhou B, Zhou H, Liu H, Zhang Y (2018) Nature differences of humic acids fractions induced by extracted sequence as explanatory factors for binding characteristics of heavy metals. Ecotoxicol Environ Saf 154:59–68
Siong F, Seng L, Nan C, Asing J, Md N, Pauzan A (2006) Characterization of the coal derived humic acids from Mukah, Sarawak as soil conditioner. J Braz Chem Soc 17:582–587. https://doi.org/10.1590/S0103-50532006000300023
Swift RS (1996) Organic matter characterization. In: Sparks DL (ed) Methods of soil analysis. Soil Science Society of America, Madison, WI, pp 1018–1020
Wei L, Li J, Xue M, Wang S, Li Q, Qin K, Jiang J, Ding J, Zhao Q (2019) Adsorption behaviors of Cu2+, Zn2+ and Cd2+ onto proteins, humic acid, and polysaccharides extracted from sludge EPS: Sorption properties and mechanisms. Bioresour Technol 291:121868. https://doi.org/10.1016/j.biortech.2019.121868
Xu J, Tan W, Xiong J, Wang MX, Koopal L (2016) Copper binding to soil fulvic and humic acids: NICA-donnan modeling and conditional affinity spectra. J Colloid Interface Sci 473:141–151. https://doi.org/10.1016/j.jcis.2016.03.066
Yan S, Zhang N, Li J, Wang Y, Liu Y, Cao M, Yan Q (2021) Characterization of humic acids from original coal and its oxidization production. Sci Rep 11:15381. https://doi.org/10.1038/s41598-021-94949-0
Funding
This research was supported and financed by the post-graduate office of the University of Guilan.
Author information
Authors and Affiliations
Contributions
Mahmood Fazeli, Sangani, Conceptualization, methodology, software, validation, data curation, writing (original draft), writing (review and editing), visualization, project administration. Akbar Forghani, Conceptualization, methodology, validation, supervision, funding acquisition. Patrycja Boguta, Validation, investigation, data curation, writing–review and editing. Marjan Anoosha, Conceptualization, methodology, lab analysis, investigation, resources, data curation. Gary Owens, Validation, investigation, resources, data curation, writing–review and editing.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Responsible editor: Anja Miltner
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Fazeli Sangani, M., Forghani, A., Boguta, P. et al. Optimal isotherm model and explanatory characteristics associated with metal ion adsorption on humic acids isolated from forest soils. J Soils Sediments 22, 2392–2405 (2022). https://doi.org/10.1007/s11368-022-03249-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11368-022-03249-1