Implications of the evolution of organic acid moieties for basalt weathering over geological time

Alexander Neaman, Jon Chorover, Susan L. Brantley

Research output: Contribution to journalReview article

74 Citations (Scopus)

Abstract

Concentrations of organic acids in prebiotic soils were presumably low, given limitations in abiotic synthesis and the limited lifetimes of organic molecules before the ultraviolet shield developed on early Earth. Prokaryotes, the first land-colonizing organisms, commonly secrete aliphatic carboxylic acids, and, less extensively, secrete aromatic compounds as siderophores and antibiotics. In contrast, secretion of aromatic acids is considerable for fungi, lichens, and vascular plants. Aromatic acids are also produced by degradation of high-molecular-weight compounds from lignin and tannin, both abundant in vascular plants. The proportion of aromatic carboxylic acids in soil solutions therefore probably increased with the evolution of higher order organisms. As biomass of organisms increased over geological, time, concentrations of organic acids in soil solutions and, in turn, the extent of ligand-promoted dissolution of minerals probably increased. To elucidate the contribution of ligands during weathering on early Earth, Columbia River basalt was dissolved under oxic and anoxic conditions in the presence (0.001 or 0.01 M) and absence of several organic ligands in batch experiments at pH 6. Release of all elements including Si was enhanced considerably in the presence of organic ligands. Citrate (tridentate) and gallate (tetradentate) increased element release to the greatest extent among the aliphatic and aromatic ligands, respectively. The extent of element mobilization observed for the aliphatic ligands decreased in the order: citrate > oxalate ≈ malonate, and for the aromatic ligands: gallate > salicylate ≈ phthalate. The effects of the ligands generally followed trends in cation-ligand stability constants, but aromatic ligands were less effective in element mobilization than aliphatic ligands. One exception was gallate, an aromatic ligand, which significantly enhanced Cu release. Ligand-promoted mobilization of Cu may therefore have increased over geological time with the increase in the proportion of aromatic ligands. In the presence of organic ligands, Fe was mobilized from basa lt considerably more than Al even under oxic conditions. Complexation of Fe with organic ligands may have mobilized Fe in Precambrian paleosols where little Al mobility is observed. Extent of P and Y release was minor in ligand-free experiments and considerable with ligands regardless of PO2. Release of Cu was considerable under oxic conditions, especially with ligands, and minor under anoxic conditions. Mobility patterns of P and Y could thus possibly serve as "organomarkers" (indicative of prevalence of organic ligands in soil solutions) and mobility patterns of Cu could possibly serve as "oxymarkers" (indicative of the presence of molecular oxygen), respectively, in ancient soils.

Original languageEnglish (US)
Pages (from-to)147-185
Number of pages39
JournalAmerican Journal of Science
Volume305
Issue number2
DOIs
StatePublished - Feb 2005

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geological time
organic acid
ligand
weathering
basalt
oxic conditions
mobilization
early Earth
carboxylic acid
vascular plant
soil
anoxic conditions
salicylate
siderophore

All Science Journal Classification (ASJC) codes

  • Earth and Planetary Sciences(all)

Cite this

@article{f307235ee83a478a83a54acb1532686a,
title = "Implications of the evolution of organic acid moieties for basalt weathering over geological time",
abstract = "Concentrations of organic acids in prebiotic soils were presumably low, given limitations in abiotic synthesis and the limited lifetimes of organic molecules before the ultraviolet shield developed on early Earth. Prokaryotes, the first land-colonizing organisms, commonly secrete aliphatic carboxylic acids, and, less extensively, secrete aromatic compounds as siderophores and antibiotics. In contrast, secretion of aromatic acids is considerable for fungi, lichens, and vascular plants. Aromatic acids are also produced by degradation of high-molecular-weight compounds from lignin and tannin, both abundant in vascular plants. The proportion of aromatic carboxylic acids in soil solutions therefore probably increased with the evolution of higher order organisms. As biomass of organisms increased over geological, time, concentrations of organic acids in soil solutions and, in turn, the extent of ligand-promoted dissolution of minerals probably increased. To elucidate the contribution of ligands during weathering on early Earth, Columbia River basalt was dissolved under oxic and anoxic conditions in the presence (0.001 or 0.01 M) and absence of several organic ligands in batch experiments at pH 6. Release of all elements including Si was enhanced considerably in the presence of organic ligands. Citrate (tridentate) and gallate (tetradentate) increased element release to the greatest extent among the aliphatic and aromatic ligands, respectively. The extent of element mobilization observed for the aliphatic ligands decreased in the order: citrate > oxalate ≈ malonate, and for the aromatic ligands: gallate > salicylate ≈ phthalate. The effects of the ligands generally followed trends in cation-ligand stability constants, but aromatic ligands were less effective in element mobilization than aliphatic ligands. One exception was gallate, an aromatic ligand, which significantly enhanced Cu release. Ligand-promoted mobilization of Cu may therefore have increased over geological time with the increase in the proportion of aromatic ligands. In the presence of organic ligands, Fe was mobilized from basa lt considerably more than Al even under oxic conditions. Complexation of Fe with organic ligands may have mobilized Fe in Precambrian paleosols where little Al mobility is observed. Extent of P and Y release was minor in ligand-free experiments and considerable with ligands regardless of PO2. Release of Cu was considerable under oxic conditions, especially with ligands, and minor under anoxic conditions. Mobility patterns of P and Y could thus possibly serve as {"}organomarkers{"} (indicative of prevalence of organic ligands in soil solutions) and mobility patterns of Cu could possibly serve as {"}oxymarkers{"} (indicative of the presence of molecular oxygen), respectively, in ancient soils.",
author = "Alexander Neaman and Jon Chorover and Brantley, {Susan L.}",
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language = "English (US)",
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Implications of the evolution of organic acid moieties for basalt weathering over geological time. / Neaman, Alexander; Chorover, Jon; Brantley, Susan L.

In: American Journal of Science, Vol. 305, No. 2, 02.2005, p. 147-185.

Research output: Contribution to journalReview article

TY - JOUR

T1 - Implications of the evolution of organic acid moieties for basalt weathering over geological time

AU - Neaman, Alexander

AU - Chorover, Jon

AU - Brantley, Susan L.

PY - 2005/2

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N2 - Concentrations of organic acids in prebiotic soils were presumably low, given limitations in abiotic synthesis and the limited lifetimes of organic molecules before the ultraviolet shield developed on early Earth. Prokaryotes, the first land-colonizing organisms, commonly secrete aliphatic carboxylic acids, and, less extensively, secrete aromatic compounds as siderophores and antibiotics. In contrast, secretion of aromatic acids is considerable for fungi, lichens, and vascular plants. Aromatic acids are also produced by degradation of high-molecular-weight compounds from lignin and tannin, both abundant in vascular plants. The proportion of aromatic carboxylic acids in soil solutions therefore probably increased with the evolution of higher order organisms. As biomass of organisms increased over geological, time, concentrations of organic acids in soil solutions and, in turn, the extent of ligand-promoted dissolution of minerals probably increased. To elucidate the contribution of ligands during weathering on early Earth, Columbia River basalt was dissolved under oxic and anoxic conditions in the presence (0.001 or 0.01 M) and absence of several organic ligands in batch experiments at pH 6. Release of all elements including Si was enhanced considerably in the presence of organic ligands. Citrate (tridentate) and gallate (tetradentate) increased element release to the greatest extent among the aliphatic and aromatic ligands, respectively. The extent of element mobilization observed for the aliphatic ligands decreased in the order: citrate > oxalate ≈ malonate, and for the aromatic ligands: gallate > salicylate ≈ phthalate. The effects of the ligands generally followed trends in cation-ligand stability constants, but aromatic ligands were less effective in element mobilization than aliphatic ligands. One exception was gallate, an aromatic ligand, which significantly enhanced Cu release. Ligand-promoted mobilization of Cu may therefore have increased over geological time with the increase in the proportion of aromatic ligands. In the presence of organic ligands, Fe was mobilized from basa lt considerably more than Al even under oxic conditions. Complexation of Fe with organic ligands may have mobilized Fe in Precambrian paleosols where little Al mobility is observed. Extent of P and Y release was minor in ligand-free experiments and considerable with ligands regardless of PO2. Release of Cu was considerable under oxic conditions, especially with ligands, and minor under anoxic conditions. Mobility patterns of P and Y could thus possibly serve as "organomarkers" (indicative of prevalence of organic ligands in soil solutions) and mobility patterns of Cu could possibly serve as "oxymarkers" (indicative of the presence of molecular oxygen), respectively, in ancient soils.

AB - Concentrations of organic acids in prebiotic soils were presumably low, given limitations in abiotic synthesis and the limited lifetimes of organic molecules before the ultraviolet shield developed on early Earth. Prokaryotes, the first land-colonizing organisms, commonly secrete aliphatic carboxylic acids, and, less extensively, secrete aromatic compounds as siderophores and antibiotics. In contrast, secretion of aromatic acids is considerable for fungi, lichens, and vascular plants. Aromatic acids are also produced by degradation of high-molecular-weight compounds from lignin and tannin, both abundant in vascular plants. The proportion of aromatic carboxylic acids in soil solutions therefore probably increased with the evolution of higher order organisms. As biomass of organisms increased over geological, time, concentrations of organic acids in soil solutions and, in turn, the extent of ligand-promoted dissolution of minerals probably increased. To elucidate the contribution of ligands during weathering on early Earth, Columbia River basalt was dissolved under oxic and anoxic conditions in the presence (0.001 or 0.01 M) and absence of several organic ligands in batch experiments at pH 6. Release of all elements including Si was enhanced considerably in the presence of organic ligands. Citrate (tridentate) and gallate (tetradentate) increased element release to the greatest extent among the aliphatic and aromatic ligands, respectively. The extent of element mobilization observed for the aliphatic ligands decreased in the order: citrate > oxalate ≈ malonate, and for the aromatic ligands: gallate > salicylate ≈ phthalate. The effects of the ligands generally followed trends in cation-ligand stability constants, but aromatic ligands were less effective in element mobilization than aliphatic ligands. One exception was gallate, an aromatic ligand, which significantly enhanced Cu release. Ligand-promoted mobilization of Cu may therefore have increased over geological time with the increase in the proportion of aromatic ligands. In the presence of organic ligands, Fe was mobilized from basa lt considerably more than Al even under oxic conditions. Complexation of Fe with organic ligands may have mobilized Fe in Precambrian paleosols where little Al mobility is observed. Extent of P and Y release was minor in ligand-free experiments and considerable with ligands regardless of PO2. Release of Cu was considerable under oxic conditions, especially with ligands, and minor under anoxic conditions. Mobility patterns of P and Y could thus possibly serve as "organomarkers" (indicative of prevalence of organic ligands in soil solutions) and mobility patterns of Cu could possibly serve as "oxymarkers" (indicative of the presence of molecular oxygen), respectively, in ancient soils.

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