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](/media/client/orcid_16x16.png)
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.
References
Aiken GR, Hsu-Kim H, Ryan JN (2011). Influence of dissolved organic matter on the environmental fate of metals, nanoparticles, and colloids. Environmental Science & Technology 45, 3196–3201.| Influence of dissolved organic matter on the environmental fate of metals, nanoparticles, and colloidsCrossref | GoogleScholarGoogle Scholar |
Avneri-Katz S, Young RB, McKenna AM, Chen H, Corilo YE, Polubesova T, Borch T, Chefetz B (2017). Adsorptive fractionation of dissolved organic matter (DOM) by mineral soil: Macroscale approach and molecular insight. Organic Geochemistry 103, 113–124.
| Adsorptive fractionation of dissolved organic matter (DOM) by mineral soil: Macroscale approach and molecular insightCrossref | GoogleScholarGoogle Scholar |
Beggs KM, Summers RS (2011). Character and chlorine reactivity of dissolved organic matter from a mountain pine beetle impacted watershed. Environmental Science & Technology 45, 5717–5724.
| Character and chlorine reactivity of dissolved organic matter from a mountain pine beetle impacted watershedCrossref | GoogleScholarGoogle Scholar |
Benedetti MF, Milne CJ, Kinniburgh DG, Van Riemsdijk WH, Koopal LK (1995). Metal ion binding to humic substances: Application of the non-ideal competitive adsorption model. Environmental Science & Technology 29, 446–457.
| Metal ion binding to humic substances: Application of the non-ideal competitive adsorption modelCrossref | GoogleScholarGoogle Scholar |
Cao X, Aiken GR, Butler KD, Mao J, Schmidt-Rohr K (2018). Comparison of the chemical composition of dissolved organic matter in three lakes in minnesota. Environmental Science & Technology 52, 1747–1755.
| Comparison of the chemical composition of dissolved organic matter in three lakes in minnesotaCrossref | GoogleScholarGoogle Scholar |
Chen C, Dynes JJ, Wang J, Sparks DL (2014). Properties of Fe-organic matter associations via coprecipitation versus adsorption. Environmental Science & Technology 48, 13751–13759.
| Properties of Fe-organic matter associations via coprecipitation versus adsorptionCrossref | GoogleScholarGoogle Scholar |
Chen W, Habibul N, Liu X-Y, Sheng G-P, Yu H-Q (2015). FTIR and synchronous fluorescence heterospectral two-dimensional correlation analyses on the binding characteristics of copper onto dissolved organic matter. Environmental Science & Technology 49, 2052–2058.
| FTIR and synchronous fluorescence heterospectral two-dimensional correlation analyses on the binding characteristics of copper onto dissolved organic matterCrossref | GoogleScholarGoogle Scholar |
Claret F, Schäfer T, Brevet J, Reiller PE (2008). Fractionation of Suwannee River fulvic acid and Aldrich humic acid on α-Al2O3: Spectroscopic evidence. Environmental Science & Technology 42, 8809–8815.
| Fractionation of Suwannee River fulvic acid and Aldrich humic acid on α-Al2O3: Spectroscopic evidenceCrossref | GoogleScholarGoogle Scholar |
Coward EK, Ohno T, Plante AF (2018). Adsorption and molecular fractionation of dissolved organic matter on iron-bearing mineral matrices of varying crystallinity. Environmental Science & Technology 52, 1036–1044.
| Adsorption and molecular fractionation of dissolved organic matter on iron-bearing mineral matrices of varying crystallinityCrossref | GoogleScholarGoogle Scholar |
Dittmar T, Koch B, Hertkorn N, Kattner G (2008). A simple and efficient method for the solid-phase extraction of dissolved organic matter (SPE-DOM) from seawater. Limnology and Oceanography: Methods 6, 230–235.
| A simple and efficient method for the solid-phase extraction of dissolved organic matter (SPE-DOM) from seawaterCrossref | GoogleScholarGoogle Scholar |
Fellman JB, Hood E, Spencer RGM (2010). Fluorescence spectroscopy opens new windows into dissolved organic matter dynamics in freshwater ecosystems: A review. Limnology and Oceanography 55, 2452–2462.
| Fluorescence spectroscopy opens new windows into dissolved organic matter dynamics in freshwater ecosystems: A reviewCrossref | GoogleScholarGoogle Scholar |
Fleury G, Del Nero M, Barillon R (2017). Effect of mineral surface properties (alumina, kaolinite) on the sorptive fractionation mechanisms of soil fulvic acids: Molecular-scale ESI-MS studies. Geochimica et Cosmochimica Acta 196, 1–17.
| Effect of mineral surface properties (alumina, kaolinite) on the sorptive fractionation mechanisms of soil fulvic acids: Molecular-scale ESI-MS studiesCrossref | GoogleScholarGoogle Scholar |
Galindo C, Del Nero M (2014). Molecular level description of the sorptive fractionation of a fulvic acid on aluminum oxide using electrospray ionization Fourier transform mass spectrometry. Environmental Science & Technology 48, 7401–7408.
| Molecular level description of the sorptive fractionation of a fulvic acid on aluminum oxide using electrospray ionization Fourier transform mass spectrometryCrossref | GoogleScholarGoogle Scholar |
Gu B, Schmitt J, Chen Z, Liang L, McCarthy JF (1994). Adsorption and desorption of natural organic matter on iron oxide: Mechanisms and models. Environmental Science & Technology 28, 38–46.
| Adsorption and desorption of natural organic matter on iron oxide: Mechanisms and modelsCrossref | GoogleScholarGoogle Scholar |
Her N, Amy G, McKnight D, Sohn J, Yoon Y (2003). Characterization of DOM as a function of MW by fluorescence EEM and HPLC-SEC using UVA, DOC, and fluorescence detection. Water Research 37, 4295–4303.
| Characterization of DOM as a function of MW by fluorescence EEM and HPLC-SEC using UVA, DOC, and fluorescence detectionCrossref | GoogleScholarGoogle Scholar | 12946913PubMed |
Illés E, Tombácz E (2003). The role of variable surface charge and surface complexation in the adsorption of humic acid on magnetite. Colloids and Surfaces A: Physicochemical and Engineering Aspects 230, 99–109.
| The role of variable surface charge and surface complexation in the adsorption of humic acid on magnetiteCrossref | GoogleScholarGoogle Scholar |
Ishii SKL, Boyer TH (2012). Behavior of reoccurring PARAFAC components in fluorescent dissolved organic matter in natural and engineered systems. Critical Reviews in Environmental Science and Technology 46, 2006–2017.
| Behavior of reoccurring PARAFAC components in fluorescent dissolved organic matter in natural and engineered systemsCrossref | GoogleScholarGoogle Scholar |
Janot N, Benedetti MF, Reiller PE (2011). Colloidal α-Al2O3, europium(III) and humic substances interactions: A macroscopic and spectroscopic study. Environmental Science & Technology 45, 3224–3230.
| Colloidal α-Al2O3, europium(III) and humic substances interactions: A macroscopic and spectroscopic studyCrossref | GoogleScholarGoogle Scholar |
Kellerman AM, Dittmar T, Kothawala DN, Tranvik LJ (2014). Chemodiversity of dissolved organic matter in lakes driven by climate and hydrology. Nature Communications 5, 3804
| Chemodiversity of dissolved organic matter in lakes driven by climate and hydrologyCrossref | GoogleScholarGoogle Scholar | 24787272PubMed |
Kellerman AM, Kothawala DN, Dittmar T, Tranvik LJ (2015). Persistence of dissolved organic matter in lakes related to its molecular characteristics. Nature Geoscience 8, 454–457.
| Persistence of dissolved organic matter in lakes related to its molecular characteristicsCrossref | GoogleScholarGoogle Scholar |
Kim S, Kramer RW, Hatcher PG (2003). Graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter, the van Krevelen diagram. Analytical Chemistry 75, 5336–5344.
| Graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter, the van Krevelen diagramCrossref | GoogleScholarGoogle Scholar | 14710810PubMed |
Koch BP, Dittmar T (2006). From mass to structure: An aromaticity index for high-resolution mass data of natural organic matter. Rapid Communications in Mass Spectrometry 20, 926–932.
| From mass to structure: An aromaticity index for high-resolution mass data of natural organic matterCrossref | GoogleScholarGoogle Scholar |
Kothawala DN, Stedmon CA, Müller RA, Weyhenmeyer GA, Köhler SJ, Tranvik LJ (2014). Control of dissolved organic matter quality: Evidence from a large-scale boreal lake survey. Global Change Biology 20, 1101–1114.
| Control of dissolved organic matter quality: Evidence from a large-scale boreal lake surveyCrossref | GoogleScholarGoogle Scholar | 24343949PubMed |
Kruger BR, Dalzell BJ, Minor EC (2011). Effect of organic matter source and salinity on dissolved organic matter isolation via ultrafiltration and solid phase extraction. Aquatic Sciences 73, 405–417.
| Effect of organic matter source and salinity on dissolved organic matter isolation via ultrafiltration and solid phase extractionCrossref | GoogleScholarGoogle Scholar |
Lang F, Egger H, Kaupenjohann M (2005). Size and shape of lead–organic associations. Colloids and Surfaces A: Physicochemical and Engineering Aspects 265, 95–103.
| Size and shape of lead–organic associationsCrossref | GoogleScholarGoogle Scholar |
Lehmann J, Kleber M (2015). The contentious nature of soil organic matter. Nature 528, 60–68.
| The contentious nature of soil organic matterCrossref | GoogleScholarGoogle Scholar | 26595271PubMed |
Linkhorst A, Dittmar T, Waska H (2017). Molecular fractionation of dissolved organic matter in a shallow subterranean estuary: The role of the iron curtain. Environmental Science & Technology 51, 1312–1320.
| Molecular fractionation of dissolved organic matter in a shallow subterranean estuary: The role of the iron curtainCrossref | GoogleScholarGoogle Scholar |
Lu Y, Allen HE (2002). Characterization of copper complexation with natural dissolved organic matter (DOM)—link to acidic moieties of DOM and competition by Ca and Mg. Water Research 36, 5083–5101.
| Characterization of copper complexation with natural dissolved organic matter (DOM)—link to acidic moieties of DOM and competition by Ca and MgCrossref | GoogleScholarGoogle Scholar | 12448557PubMed |
Lv J, Zhang S, Luo L, Cao D (2016a). Solid-phase extraction-stepwise elution (SPE-SE) procedure for isolation of dissolved organic matter prior to ESI-FT-ICR-MS analysis. Analytica Chimica Acta 948, 55–61.
| Solid-phase extraction-stepwise elution (SPE-SE) procedure for isolation of dissolved organic matter prior to ESI-FT-ICR-MS analysisCrossref | GoogleScholarGoogle Scholar | 27871610PubMed |
Lv J, Zhang S, Wang S, Luo L, Cao D, Christie P (2016b). Molecular-scale investigation with ESI-FT-ICR-MS on fractionation of dissolved organic matter induced by adsorption on iron oxyhydroxides. Environmental Science & Technology 50, 2328–2336.
| Molecular-scale investigation with ESI-FT-ICR-MS on fractionation of dissolved organic matter induced by adsorption on iron oxyhydroxidesCrossref | GoogleScholarGoogle Scholar |
Lv J, Han R, Huang Z, Luo L, Cao D, Zhang S (2018a). Relationship between molecular components and reducing capacities of humic substances. ACS Earth & Space Chemistry 2, 330–339.
| Relationship between molecular components and reducing capacities of humic substancesCrossref | GoogleScholarGoogle Scholar |
Lv J, Miao Y, Huang Z, Han R, Zhang S (2018b). Facet-mediated adsorption and molecular fractionation of humic substances on hematite surfaces. Environmental Science & Technology 52, 11660–11669.
| Facet-mediated adsorption and molecular fractionation of humic substances on hematite surfacesCrossref | GoogleScholarGoogle Scholar |
Majzik A, Tombácz E (2007). Interaction between humic acid and montmorillonite in the presence of calcium ions I. Interfacial and aqueous phase equilibria: Adsorption and complexation. Organic Geochemistry 38, 1319–1329.
| Interaction between humic acid and montmorillonite in the presence of calcium ions I. Interfacial and aqueous phase equilibria: Adsorption and complexationCrossref | GoogleScholarGoogle Scholar |
Meier M, Namjesnik-Dejanovic K, Maurice PA, Chin Y-P, Aiken GR (1999). Fractionation of aquatic natural organic matter upon sorption to goethite and kaolinite. Chemical Geology 157, 275–284.
| Fractionation of aquatic natural organic matter upon sorption to goethite and kaoliniteCrossref | GoogleScholarGoogle Scholar |
Ohno T, He Z, Sleighter RL, Honeycutt CW, Hatcher PG (2010). Ultrahigh resolution mass spectrometry and indicator species analysis to identify marker components of soil- and plant biomass-derived organic matter fractions. Environmental Science & Technology 44, 8594–8600.
| Ultrahigh resolution mass spectrometry and indicator species analysis to identify marker components of soil- and plant biomass-derived organic matter fractionsCrossref | GoogleScholarGoogle Scholar |
Peng L, Liu P, Feng X, Wang Z, Cheng T, Liang Y, Lin Z, Shi Z (2018a). Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation. Geochimica et Cosmochimica Acta 224, 282–300.
| Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciationCrossref | GoogleScholarGoogle Scholar |
Peng S, Wang P, Peng L, Cheng T, Sun W, Shi Z (2018b). Predicting heavy metal partition equilibrium in soils: Roles of soil components and binding sites. Soil Science Society of America Journal 82, 839–849.
| Predicting heavy metal partition equilibrium in soils: Roles of soil components and binding sitesCrossref | GoogleScholarGoogle Scholar |
Philippe A, Schaumann GE (2014). Interactions of dissolved organic matter with natural and engineered inorganic colloids: A review. Environmental Science & Technology 48, 8946–8962.
| Interactions of dissolved organic matter with natural and engineered inorganic colloids: A reviewCrossref | GoogleScholarGoogle Scholar |
Polubesova T, Chefetz B (2014). DOM-affected transformation of contaminants on mineral surfaces: A review. Critical Reviews in Environmental Science and Technology 44, 223–254.
| DOM-affected transformation of contaminants on mineral surfaces: A reviewCrossref | GoogleScholarGoogle Scholar |
Riedel T, Biester H, Dittmar T (2012). Molecular fractionation of dissolved organic matter with metal salts. Environmental Science & Technology 46, 4419–4426.
| Molecular fractionation of dissolved organic matter with metal saltsCrossref | GoogleScholarGoogle Scholar |
Römkens PFAM, Dolfing J (1998). Effect of Ca on the solubility and molecular size distribution of DOC and Cu binding in soil solution samples. Environmental Science & Technology 32, 363–369.
| Effect of Ca on the solubility and molecular size distribution of DOC and Cu binding in soil solution samplesCrossref | GoogleScholarGoogle Scholar |
Schlautman MA, Morgan JJ (1994). Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry. Geochimica et Cosmochimica Acta 58, 4293–4303.
| Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistryCrossref | GoogleScholarGoogle Scholar |
Schmidt MWI, Torn MS, Abiven S, Dittmar T, Guggenberger G, Janssens IA, Kleber M, Kögel-Knabner I, Lehmann J, Manning DAC, Nannipieri P, Rasse DP, Weiner S, Trumbore SE (2011). Persistence of soil organic matter as an ecosystem property. Nature 478, 49–56.
| Persistence of soil organic matter as an ecosystem propertyCrossref | GoogleScholarGoogle Scholar |
Schwertmann UC, Cornell RM (2000). ‘Iron oxides in the laboratory: preparation and characterization, 2nd edn.’ (Wiley-VCH: Weinheim)
Shi Z, Wang P, Peng L, Lin Z, Dang Z (2016). Kinetics of heavy metal dissociation from natural organic matter: Roles of the carboxylic and phenolic sites. Environmental Science & Technology 50, 10476–10484.
| Kinetics of heavy metal dissociation from natural organic matter: Roles of the carboxylic and phenolic sitesCrossref | GoogleScholarGoogle Scholar |
Sowers TD, Adhikari D, Wang J, Yang Y, Sparks DL (2018a). Spatial associations and chemical composition of organic carbon sequestered in Fe, Ca, and organic carbon ternary systems. Environmental Science & Technology 52, 6936–6944.
| Spatial associations and chemical composition of organic carbon sequestered in Fe, Ca, and organic carbon ternary systemsCrossref | GoogleScholarGoogle Scholar |
Sowers TD, Stuckey JW, Sparks DL (2018b). The synergistic effect of calcium on organic carbon sequestration to ferrihydrite. Geochemical Transactions 19, 4
| The synergistic effect of calcium on organic carbon sequestration to ferrihydriteCrossref | GoogleScholarGoogle Scholar | 29397451PubMed |
Stedmon CA, Bro R (2008). Characterizing dissolved organic matter fluorescence with parallel factor analysis: A tutorial. Limnology and Oceanography: Methods 6, 572–579.
| Characterizing dissolved organic matter fluorescence with parallel factor analysis: A tutorialCrossref | GoogleScholarGoogle Scholar |
Stenson AC, Marshall AG, Cooper WT (2003). Exact masses and chemical formulas of individual Suwannee River fulvic acids from ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectra. Analytical Chemistry 75, 1275–1284.
| Exact masses and chemical formulas of individual Suwannee River fulvic acids from ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectraCrossref | GoogleScholarGoogle Scholar | 12659186PubMed |
Sutton R, Sposito G (2005). Molecular structure in soil humic substances: The new view. Environmental Science & Technology 39, 9009–9015.
| Molecular structure in soil humic substances: The new viewCrossref | GoogleScholarGoogle Scholar |
Tfaily MM, Hamdan R, Corbett JE, Chanton JP, Glaser PH, Cooper WT (2013). Investigating dissolved organic matter decomposition in northern peatlands using complimentary analytical techniques. Geochimica et Cosmochimica Acta 112, 116–129.
| Investigating dissolved organic matter decomposition in northern peatlands using complimentary analytical techniquesCrossref | GoogleScholarGoogle Scholar |
Tfaily MM, Chu RK, Tolić N, Roscioli KM, Anderton CR, Paša-Tolić L, Robinson EW, Hess NJ (2015). Advanced solvent based methods for molecular characterization of soil organic matter by high-resolution mass spectrometry. Analytical Chemistry 87, 5206–5215.
| Advanced solvent based methods for molecular characterization of soil organic matter by high-resolution mass spectrometryCrossref | GoogleScholarGoogle Scholar | 25884232PubMed |
Weng L, Van Riemsdijk WH, Hiemstra T (2007). Adsorption of humic acids onto goethite: Effects of molar mass, pH and ionic strength. Journal of Colloid and Interface Science 314, 107–118.
| Adsorption of humic acids onto goethite: Effects of molar mass, pH and ionic strengthCrossref | GoogleScholarGoogle Scholar | 17588595PubMed |
Yan M, Gregory VK (2014). Comparative examination of effects of binding of different metals on chromophores of dissolved organic matter. Environmental Science & Technology 48, 3177–3185.
| Comparative examination of effects of binding of different metals on chromophores of dissolved organic matterCrossref | GoogleScholarGoogle Scholar |
Young BR, Avneri-Katz S, McKenna MA, Chen H, Bahureksa W, Polubesova T, Chefetz B, Borch T (2018). Composition-dependent sorptive fractionation of anthropogenic dissolved organic matter by Fe(III)-montmorillonite. Soil Systems 2, 14
| Composition-dependent sorptive fractionation of anthropogenic dissolved organic matter by Fe(III)-montmorilloniteCrossref | GoogleScholarGoogle Scholar |