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RESEARCH ARTICLE

Molecular fractionation of dissolved organic matter on ferrihydrite: effects of dissolved cations

Minqin Liu A B , Yang Ding A B , Shimeng Peng A B , Yang Lu A B , Zhi Dang A B and Zhenqing Shi https://orcid.org/0000-0003-3131-3248 A B C
+ Author Affiliations
- Author Affiliations

A School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, China.

B The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, South China University of Technology, Guangzhou, Guangdong 510006, China.

C Corresponding author. Email: zqshi@scut.edu.cn

Environmental Chemistry 16(2) 137-148 https://doi.org/10.1071/EN18235
Submitted: 3 November 2018  Accepted: 29 December 2018   Published: 25 January 2019

Environmental context. Carbon sequestration and dynamics are influenced by adsorptive fractionation of dissolved organic matter (DOM) on minerals. We found that the molecular fractionation of DOM on ferrihydrite was highly dependent on the presence of Na, Ca and Cu ions in water. These results advance our mechanistic understanding of the dynamic behaviour of DOM, and contribute to predicting carbon cycling and contaminant behaviour in the natural environment.

Abstract. The adsorptive fractionation of dissolved organic matter (DOM) at the ferrihydrite and water interface is a key geochemical process controlling DOM compositions and reactivity, thus affecting carbon cycling and contaminant behaviour in the environment. However, the effects of cations on DOM fractionation and the underlying mechanisms are poorly understood. In this study, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with spectroscopic methods were employed to investigate molecular fractionation of DOM on ferrihydrite under different cations in the background electrolytes, including Na, Ca, and Cu ions. The results indicated that DOM fractionation was influenced by the combined effects of cation type, intrinsic molecular property, and extent of DOM adsorption. DOM adsorption on ferrihydrite exhibited the strongest and the weakest fractionation under Na and Ca background electrolytes, respectively. Both Ca and Cu background electrolytes reduced the adsorption of highly unsaturated and phenolic/polyphenolic molecules with high molecular weight and number of O atoms. In addition to the molecular acidity, the complexation of Ca and Cu ions to DOM binding sites and the coagulation effect of divalent cations may affect molecular fractionation. Additionally, DOM fractionation was enhanced with increasing DOM adsorption. Our results contribute to predicting carbon cycling and contaminant behaviour in the natural environment.

Additional keywords: adsorption, FT-ICR-MS.


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