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Deciphering Competitive Interactions of Natural Organic Matter Components at Metal Oxides: Insights from Experiments and Modeling.

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Title: Deciphering Competitive Interactions of Natural Organic Matter Components at Metal Oxides: Insights from Experiments and Modeling.
Authors: Xu Y; Soil Chemistry and Chemical Soil Quality Group, Wageningen University & Research, Wageningen 6708 PB, The Netherlands.; State Environmental Protection Key Laboratory of Soil Health and Green Remediation, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China., Hiemstra T; Soil Chemistry and Chemical Soil Quality Group, Wageningen University & Research, Wageningen 6708 PB, The Netherlands., Bai Y; Soil Chemistry and Chemical Soil Quality Group, Wageningen University & Research, Wageningen 6708 PB, The Netherlands.; Chongqing Academy of Agriculture Sciences, Chongqing 40000, China., Tan W; State Environmental Protection Key Laboratory of Soil Health and Green Remediation, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China., Weng L; Soil Chemistry and Chemical Soil Quality Group, Wageningen University & Research, Wageningen 6708 PB, The Netherlands.; Agro-Environmental Protection Institute, Ministry of Agriculture, Tianjin 300191, P. R. China.
Source: Environmental science & technology [Environ Sci Technol] 2025 Nov 11; Vol. 59 (44), pp. 23849-23858. Date of Electronic Publication: 2025 Oct 30.
Publication Type: Journal Article
Language: English
Journal Info: Publisher: American Chemical Society Country of Publication: United States NLM ID: 0213155 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5851 (Electronic) Linking ISSN: 0013936X NLM ISO Abbreviation: Environ Sci Technol Subsets: MEDLINE
Imprint Name(s): Publication: Washington DC : American Chemical Society
Original Publication: Easton, Pa. : American Chemical Society, c1967-
MeSH Terms: Metals*, Humic Substances ; Adsorption ; Benzopyrans ; Oxides/chemistry ; Minerals ; Iron Compounds/chemistry
Abstract: Natural organic matter (NOM) is a heterogeneous mixture, including humic acid (HA) and fulvic acid (FA), that competitively interacts with metal (hydr)oxides. Despite its environmental importance, this competition has not yet been measured extensively, and mechanistic modeling is lacking. The present work examined the competitive adsorption to goethite and the corresponding molecular fractionation of HA and FA using UV-vis spectroscopy, acid precipitation, and size exclusion chromatography (SEC). Our findings reveal that on a mass basis, FA particles effectively remove HA particles from the surface. This efficiency can be mainly attributed to an interfacial space limitation in which FA restricts HA adsorption, as evidenced by mechanistic modeling with the Consistent Competitive Ligand and Charge Distribution (LCD cc ) approach for the heterogeneous adsorption of NOM. The adsorbed FA particles occupying part of the surface prevent HA from accessing the corresponding double-layer space, disproportionally reducing HA adsorption. This restriction leads to a high HA/FA mass exchange ratio (∼2.4 ± 0.6), consequently affecting the mobility and transport of oxyanions (arsenate and phosphate) in the environment. The difference in the partitioning of NOM is also relevant for soil carbon sequestration via the selective preservation of NOM by association with oxide minerals.
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Contributed Indexing: Keywords: LCDcc model; adsorption volume; competitive adsorption; heterogeneity; iron oxide; molecular fractionation
Substance Nomenclature: 0 (Humic Substances)
XII14C5FXV (fulvic acid)
0 (Benzopyrans)
0 (Oxides)
0 (Minerals)
0 (Metals)
1310-14-1 (goethite)
0 (Iron Compounds)
Entry Date(s): Date Created: 20251030 Date Completed: 20251112 Latest Revision: 20251115
Update Code: 20251115
PubMed Central ID: PMC12613805
DOI: 10.1021/acs.est.5c00782
PMID: 41165211
Database: MEDLINE
Description
Abstract:Natural organic matter (NOM) is a heterogeneous mixture, including humic acid (HA) and fulvic acid (FA), that competitively interacts with metal (hydr)oxides. Despite its environmental importance, this competition has not yet been measured extensively, and mechanistic modeling is lacking. The present work examined the competitive adsorption to goethite and the corresponding molecular fractionation of HA and FA using UV-vis spectroscopy, acid precipitation, and size exclusion chromatography (SEC). Our findings reveal that on a mass basis, FA particles effectively remove HA particles from the surface. This efficiency can be mainly attributed to an interfacial space limitation in which FA restricts HA adsorption, as evidenced by mechanistic modeling with the Consistent Competitive Ligand and Charge Distribution (LCD <subscript>cc</subscript> ) approach for the heterogeneous adsorption of NOM. The adsorbed FA particles occupying part of the surface prevent HA from accessing the corresponding double-layer space, disproportionally reducing HA adsorption. This restriction leads to a high HA/FA mass exchange ratio (∼2.4 ± 0.6), consequently affecting the mobility and transport of oxyanions (arsenate and phosphate) in the environment. The difference in the partitioning of NOM is also relevant for soil carbon sequestration via the selective preservation of NOM by association with oxide minerals.
ISSN:1520-5851
DOI:10.1021/acs.est.5c00782