Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive Transport

Sorptive retention of dissolved organic matter (DOM) at soil particle surfaces controls C flux through the critical zone. Prior studies have shown that pristine Al‐ and Fe‐(oxy)hydroxide surfaces are especially reactive toward DOM sorptive stabilization. However, the impact of progressive and/or pre...

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Main Authors: Angélica Vázquez-Ortega, Selene Hernandez-Ruiz, Mary Kay Amistadi, Craig Rasmussen, Jon Chorover
Format: Article
Language:English
Published: Wiley 2014-07-01
Series:Vadose Zone Journal
Online Access:https://doi.org/10.2136/vzj2013.10.0179
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author Angélica Vázquez-Ortega
Selene Hernandez-Ruiz
Mary Kay Amistadi
Craig Rasmussen
Jon Chorover
author_facet Angélica Vázquez-Ortega
Selene Hernandez-Ruiz
Mary Kay Amistadi
Craig Rasmussen
Jon Chorover
author_sort Angélica Vázquez-Ortega
collection DOAJ
description Sorptive retention of dissolved organic matter (DOM) at soil particle surfaces controls C flux through the critical zone. Prior studies have shown that pristine Al‐ and Fe‐(oxy)hydroxide surfaces are especially reactive toward DOM sorptive stabilization. However, the impact of progressive and/or preexisting organic surface coatings on further surficial uptake and exchange during repeated DOM infusion episodes remains unclear. In this study, DOM solutions were extracted from organic horizons in grassland (G) and mixed conifer forest (F) vegetation types in the Jemez River Basin Critical Zone Observatory. Extracted DOM solutions were used to sequentially irrigate columns packed with either quartz sand (Qtz), Al‐hydroxide‐coated quartz sand (Al‐Qtz), or Fe‐hydroxide‐coated quartz sand (Fe‐Qtz). Use of distinct DOM sources enabled investigation of how sorption, fractionation, and exchange ensued during reactive transport through mineral media progressively coated with sorbate organic matter (SOM). During initial irrigation of fresh mineral media with G‐DOM, the magnitude of DOM sorption (per unit sorbent mass) followed the trend: Al‐Qtz ≥ Fe‐Qtz > Qtz. Effluent solutions showed diminished molar absorptivity and humification index (HIX) values, indicating preferential uptake of high‐molar‐mass aromatic constituents. Introduction of F‐DOM to G‐SOM‐coated surfaces revealed competitive desorption of G‐SOM from the organo–mineral interface. During F‐DOM irrigation, high HIX values were observed in effluent solutions, indicating remobilization of G‐SOM by displacement. According to spectroscopic analyses, the displaced G‐SOM consisted of aromatic phenolic acids with high excitation–emission “fingerprints” characteristic of fulvic‐ and humic‐acid‐like compounds, providing evidence for kinetic DOM exchange reactions.
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spelling doaj.art-076228aac1464d468d311bf9303db4342023-07-27T06:11:13ZengWileyVadose Zone Journal1539-16632014-07-0113711310.2136/vzj2013.10.0179Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive TransportAngélica Vázquez-Ortega0Selene Hernandez-Ruiz1Mary Kay Amistadi2Craig Rasmussen3Jon Chorover4Dep. of Soil, Water & Environmental ScienceUniv. of ArizonaP.O. Box 210038TucsonAZ85721‐0038Dep. of Soil, Water & Environmental ScienceUniv. of ArizonaP.O. Box 210038TucsonAZ85721‐0038Dep. of Soil, Water & Environmental ScienceUniv. of ArizonaP.O. Box 210038TucsonAZ85721‐0038Dep. of Soil, Water & Environmental ScienceUniv. of ArizonaP.O. Box 210038TucsonAZ85721‐0038Dep. of Soil, Water & Environmental ScienceUniv. of ArizonaP.O. Box 210038TucsonAZ85721‐0038Sorptive retention of dissolved organic matter (DOM) at soil particle surfaces controls C flux through the critical zone. Prior studies have shown that pristine Al‐ and Fe‐(oxy)hydroxide surfaces are especially reactive toward DOM sorptive stabilization. However, the impact of progressive and/or preexisting organic surface coatings on further surficial uptake and exchange during repeated DOM infusion episodes remains unclear. In this study, DOM solutions were extracted from organic horizons in grassland (G) and mixed conifer forest (F) vegetation types in the Jemez River Basin Critical Zone Observatory. Extracted DOM solutions were used to sequentially irrigate columns packed with either quartz sand (Qtz), Al‐hydroxide‐coated quartz sand (Al‐Qtz), or Fe‐hydroxide‐coated quartz sand (Fe‐Qtz). Use of distinct DOM sources enabled investigation of how sorption, fractionation, and exchange ensued during reactive transport through mineral media progressively coated with sorbate organic matter (SOM). During initial irrigation of fresh mineral media with G‐DOM, the magnitude of DOM sorption (per unit sorbent mass) followed the trend: Al‐Qtz ≥ Fe‐Qtz > Qtz. Effluent solutions showed diminished molar absorptivity and humification index (HIX) values, indicating preferential uptake of high‐molar‐mass aromatic constituents. Introduction of F‐DOM to G‐SOM‐coated surfaces revealed competitive desorption of G‐SOM from the organo–mineral interface. During F‐DOM irrigation, high HIX values were observed in effluent solutions, indicating remobilization of G‐SOM by displacement. According to spectroscopic analyses, the displaced G‐SOM consisted of aromatic phenolic acids with high excitation–emission “fingerprints” characteristic of fulvic‐ and humic‐acid‐like compounds, providing evidence for kinetic DOM exchange reactions.https://doi.org/10.2136/vzj2013.10.0179
spellingShingle Angélica Vázquez-Ortega
Selene Hernandez-Ruiz
Mary Kay Amistadi
Craig Rasmussen
Jon Chorover
Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive Transport
Vadose Zone Journal
title Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive Transport
title_full Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive Transport
title_fullStr Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive Transport
title_full_unstemmed Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive Transport
title_short Fractionation of Dissolved Organic Matter by (Oxy)Hydroxide‐Coated Sands: Competitive Sorbate Displacement during Reactive Transport
title_sort fractionation of dissolved organic matter by oxy hydroxide coated sands competitive sorbate displacement during reactive transport
url https://doi.org/10.2136/vzj2013.10.0179
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