Mineral mesopore effects on nitrogenous organic matter adsorption

Andrew R. Zimmerman, Keith W. Goyne, Jon Chorover, Sridhar Komarneni, Susan L. Brantley

Research output: Contribution to journalArticle

88 Citations (Scopus)

Abstract

The "mesopore protection hypothesis" [Chem. Geol. 114 (1994) 347; Geochim. Cosmochim. Acta 58 (1994) 1271] proposes that organic matter (OM) may be protected from enzymatic degradation by sequestration within mineral mesopores (2-50 nm diameter). This hypothesis is a leading, though controversial, theory in explaining both the preservation of some extremely labile OM compounds and observed correlations between OM content and mineral surface area in soils and sediments. To test this idea, we carried out batch experiments in aqueous suspensions to examine the adsorption/desorption of amino acid monomers and polymers onto fabricated mesoporous and nonporous alumina and silica. Each mineral pair was of similar surface chemistry and differed only in the presence or absence of intraparticle mesoporosity. All amino acid monomers and polymers smaller than about one-half the pore diameter exhibited significantly greater surface area-normalized adsorption to mesoporous alumina (8.2 nm mean pore diameter) and silica (3.4 nm mean pore diameter) compared to nonporous mineral analogues. Proteins larger than the mesopores exhibited greater adsorption to the nonporous phases indicating their exclusion from internal surfaces of mesoporous minerals. Greater desorption hysteresis for mesopore-sorbed OM indicates that desorption from pores was inhibited. The adsorption/desorption data, as well as Langmuir-Freundlich modeling and adsorption affinity distributions, suggest that capillary condensation, a 'pore-filling' mechanism, may explain the experimental observations. These results provide a potential mechanism for the selective sequestration and preservation of sedimentary OM as well as organic contaminants.

Original languageEnglish (US)
Pages (from-to)355-375
Number of pages21
JournalOrganic Geochemistry
Volume35
Issue number3
DOIs
StatePublished - Mar 2004

Fingerprint

Biological materials
Minerals
Desorption
desorption
adsorption
Adsorption
organic matter
mineral
Aluminum Oxide
Silicon Dioxide
aluminum oxide
Polymers
polymer
surface area
amino acid
silica
Monomers
Amino Acids
Surface chemistry
hysteresis

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

Mineral mesopore effects on nitrogenous organic matter adsorption. / Zimmerman, Andrew R.; Goyne, Keith W.; Chorover, Jon; Komarneni, Sridhar; Brantley, Susan L.

In: Organic Geochemistry, Vol. 35, No. 3, 03.2004, p. 355-375.

Research output: Contribution to journalArticle

Zimmerman, Andrew R. ; Goyne, Keith W. ; Chorover, Jon ; Komarneni, Sridhar ; Brantley, Susan L. / Mineral mesopore effects on nitrogenous organic matter adsorption. In: Organic Geochemistry. 2004 ; Vol. 35, No. 3. pp. 355-375.
@article{7c23187594664867b22a3dd9e0662f74,
title = "Mineral mesopore effects on nitrogenous organic matter adsorption",
abstract = "The {"}mesopore protection hypothesis{"} [Chem. Geol. 114 (1994) 347; Geochim. Cosmochim. Acta 58 (1994) 1271] proposes that organic matter (OM) may be protected from enzymatic degradation by sequestration within mineral mesopores (2-50 nm diameter). This hypothesis is a leading, though controversial, theory in explaining both the preservation of some extremely labile OM compounds and observed correlations between OM content and mineral surface area in soils and sediments. To test this idea, we carried out batch experiments in aqueous suspensions to examine the adsorption/desorption of amino acid monomers and polymers onto fabricated mesoporous and nonporous alumina and silica. Each mineral pair was of similar surface chemistry and differed only in the presence or absence of intraparticle mesoporosity. All amino acid monomers and polymers smaller than about one-half the pore diameter exhibited significantly greater surface area-normalized adsorption to mesoporous alumina (8.2 nm mean pore diameter) and silica (3.4 nm mean pore diameter) compared to nonporous mineral analogues. Proteins larger than the mesopores exhibited greater adsorption to the nonporous phases indicating their exclusion from internal surfaces of mesoporous minerals. Greater desorption hysteresis for mesopore-sorbed OM indicates that desorption from pores was inhibited. The adsorption/desorption data, as well as Langmuir-Freundlich modeling and adsorption affinity distributions, suggest that capillary condensation, a 'pore-filling' mechanism, may explain the experimental observations. These results provide a potential mechanism for the selective sequestration and preservation of sedimentary OM as well as organic contaminants.",
author = "Zimmerman, {Andrew R.} and Goyne, {Keith W.} and Jon Chorover and Sridhar Komarneni and Brantley, {Susan L.}",
year = "2004",
month = "3",
doi = "10.1016/j.orggeochem.2003.10.009",
language = "English (US)",
volume = "35",
pages = "355--375",
journal = "Organic Geochemistry",
issn = "0146-6380",
publisher = "Elsevier Limited",
number = "3",

}

TY - JOUR

T1 - Mineral mesopore effects on nitrogenous organic matter adsorption

AU - Zimmerman, Andrew R.

AU - Goyne, Keith W.

AU - Chorover, Jon

AU - Komarneni, Sridhar

AU - Brantley, Susan L.

PY - 2004/3

Y1 - 2004/3

N2 - The "mesopore protection hypothesis" [Chem. Geol. 114 (1994) 347; Geochim. Cosmochim. Acta 58 (1994) 1271] proposes that organic matter (OM) may be protected from enzymatic degradation by sequestration within mineral mesopores (2-50 nm diameter). This hypothesis is a leading, though controversial, theory in explaining both the preservation of some extremely labile OM compounds and observed correlations between OM content and mineral surface area in soils and sediments. To test this idea, we carried out batch experiments in aqueous suspensions to examine the adsorption/desorption of amino acid monomers and polymers onto fabricated mesoporous and nonporous alumina and silica. Each mineral pair was of similar surface chemistry and differed only in the presence or absence of intraparticle mesoporosity. All amino acid monomers and polymers smaller than about one-half the pore diameter exhibited significantly greater surface area-normalized adsorption to mesoporous alumina (8.2 nm mean pore diameter) and silica (3.4 nm mean pore diameter) compared to nonporous mineral analogues. Proteins larger than the mesopores exhibited greater adsorption to the nonporous phases indicating their exclusion from internal surfaces of mesoporous minerals. Greater desorption hysteresis for mesopore-sorbed OM indicates that desorption from pores was inhibited. The adsorption/desorption data, as well as Langmuir-Freundlich modeling and adsorption affinity distributions, suggest that capillary condensation, a 'pore-filling' mechanism, may explain the experimental observations. These results provide a potential mechanism for the selective sequestration and preservation of sedimentary OM as well as organic contaminants.

AB - The "mesopore protection hypothesis" [Chem. Geol. 114 (1994) 347; Geochim. Cosmochim. Acta 58 (1994) 1271] proposes that organic matter (OM) may be protected from enzymatic degradation by sequestration within mineral mesopores (2-50 nm diameter). This hypothesis is a leading, though controversial, theory in explaining both the preservation of some extremely labile OM compounds and observed correlations between OM content and mineral surface area in soils and sediments. To test this idea, we carried out batch experiments in aqueous suspensions to examine the adsorption/desorption of amino acid monomers and polymers onto fabricated mesoporous and nonporous alumina and silica. Each mineral pair was of similar surface chemistry and differed only in the presence or absence of intraparticle mesoporosity. All amino acid monomers and polymers smaller than about one-half the pore diameter exhibited significantly greater surface area-normalized adsorption to mesoporous alumina (8.2 nm mean pore diameter) and silica (3.4 nm mean pore diameter) compared to nonporous mineral analogues. Proteins larger than the mesopores exhibited greater adsorption to the nonporous phases indicating their exclusion from internal surfaces of mesoporous minerals. Greater desorption hysteresis for mesopore-sorbed OM indicates that desorption from pores was inhibited. The adsorption/desorption data, as well as Langmuir-Freundlich modeling and adsorption affinity distributions, suggest that capillary condensation, a 'pore-filling' mechanism, may explain the experimental observations. These results provide a potential mechanism for the selective sequestration and preservation of sedimentary OM as well as organic contaminants.

UR - http://www.scopus.com/inward/record.url?scp=1442291172&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=1442291172&partnerID=8YFLogxK

U2 - 10.1016/j.orggeochem.2003.10.009

DO - 10.1016/j.orggeochem.2003.10.009

M3 - Article

AN - SCOPUS:1442291172

VL - 35

SP - 355

EP - 375

JO - Organic Geochemistry

JF - Organic Geochemistry

SN - 0146-6380

IS - 3

ER -