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LCZO -- Soil Redox Potential, Soil Biogeochemistry -- Fe speciation, redox -- Luquillo Mountains -- (2016-2018)


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Abstract

While the contribution of iron (Fe)-bearing minerals to organic carbon (C) stabilization in terrestrial systems is well-described, the influence of Fe solid-phase speciation on organomineral associations is unclear in highly dynamic, oxidation-reduction (redox)-active soils. In humid tropic forest soils, fluctuations in redox state accelerate weathering of Fe-bearing mineral phases, producing a spectrum of mineral sizes and bonding environments available for C stabilization, and confounding our understanding of C stability. Characterizing these Fe-bearing phases can improve predictions of the response of redox-active soil systems to climatic changes that may alter Fe mineral crystallinity and solubility, such as precipitation intensity, storm event frequency and temperature. Leveraging inorganic selective dissolution techniques, 57Fe Mössbauer spectroscopy (MBS), specific surface area (SSA) analyses and X-ray diffraction (XRD), we investigated mineral speciation in surface soils of contrasting lithologies from the Luquillo Critical Zone Observatory (LCZO), Puerto Rico. The LCZO provides a model investigatory framework in which high C inputs to surface horizons by similar vegetation, topography and climatic forcings are intercepted by highly-weathered, volcaniclastic Oxisols or quartz diorite-derived Inceptisols, producing a gradient of Fe content and speciation. Strong correlations observed between Fe concentrations and extraction-induced changes in SSA indicated target Fe phases contribute substantially to SSA of the bulk mineral matrix. MBS analysis of untreated soils reveal both Oxisol and Inceptisol soils are largely composed of FeIII-oxyhydroxides, accompanied by substantial FeII and silicate FeIII contributions in Inceptisol soils. FeIII-oxyhydroxides in the Oxisol soils were largely short-range-ordered (SRO), and notably, a fraction of particularly low-crystallinity FeIII-oxyhydroxide mineral phases in these soils appear protected against harsh reductive dissolution, whereas the overall higher crystallinity Fe phases in the Inceptisol soils do not. These findings suggest that some high-SSA, SRO FeIII phases, which likely also have high C sorption capacities, may be immobilized against reduction in these Oxisol soils. Consequently, C associated with these FeIII phases may be preferentially stabilized in Oxisol soils, potentially driving disparate C mineralization and CO2 production rates across contrasting lithologies.

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Resource Level Coverage

Spatial

Coordinate System/Geographic Projection:
WGS 84 EPSG:4326
Coordinate Units:
Decimal degrees
Place/Area Name:
Northeastern Puerto Rico and the Luquillo Mountains, Luquillo Mountains
North Latitude
18.3610°
East Longitude
-65.6921°
South Latitude
18.2267°
West Longitude
-65.8514°

Temporal

Start Date:
End Date:

Content

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LCZO -- Soil Redox Potential, Soil Biogeochemistry -- Fe speciation, redox -- Luquillo Mountains -- (2016-2018)


OVERVIEW

Description/Abstract

While the contribution of iron (Fe)-bearing minerals to organic carbon (C) stabilization in terrestrial systems is well-described, the influence of Fe solid-phase speciation on organomineral associations is unclear in highly dynamic, oxidation-reduction (redox)-active soils. In humid tropic forest soils, fluctuations in redox state accelerate weathering of Fe-bearing mineral phases, producing a spectrum of mineral sizes and bonding environments available for C stabilization, and confounding our understanding of C stability. Characterizing these Fe-bearing phases can improve predictions of the response of redox-active soil systems to climatic changes that may alter Fe mineral crystallinity and solubility, such as precipitation intensity, storm event frequency and temperature. Leveraging inorganic selective dissolution techniques, 57Fe Mössbauer spectroscopy (MBS), specific surface area (SSA) analyses and X-ray diffraction (XRD), we investigated mineral speciation in surface soils of contrasting lithologies from the Luquillo Critical Zone Observatory (LCZO), Puerto Rico. The LCZO provides a model investigatory framework in which high C inputs to surface horizons by similar vegetation, topography and climatic forcings are intercepted by highly-weathered, volcaniclastic Oxisols or quartz diorite-derived Inceptisols, producing a gradient of Fe content and speciation. Strong correlations observed between Fe concentrations and extraction-induced changes in SSA indicated target Fe phases contribute substantially to SSA of the bulk mineral matrix. MBS analysis of untreated soils reveal both Oxisol and Inceptisol soils are largely composed of FeIII-oxyhydroxides, accompanied by substantial FeII and silicate FeIII contributions in Inceptisol soils. FeIII-oxyhydroxides in the Oxisol soils were largely short-range-ordered (SRO), and notably, a fraction of particularly low-crystallinity FeIII-oxyhydroxide mineral phases in these soils appear protected against harsh reductive dissolution, whereas the overall higher crystallinity Fe phases in the Inceptisol soils do not. These findings suggest that some high-SSA, SRO FeIII phases, which likely also have high C sorption capacities, may be immobilized against reduction in these Oxisol soils. Consequently, C associated with these FeIII phases may be preferentially stabilized in Oxisol soils, potentially driving disparate C mineralization and CO2 production rates across contrasting lithologies.

Creator/Author

Elizabeth K. Coward|Aaron Thompson|Alain F. Plante

CZOs

Luquillo

Contact

Miguel Leon, Miguel.Leon@unh.edu

Subtitle

Contrasting Fe speciation in two humid forest soils: Insight into organomineral complexation in redox-active environments




SUBJECTS

Disciplines

Biogeochemistry|Soil Science / Pedology

Topics

Soil Redox Potential|Soil Biogeochemistry

Subtopic

Fe speciation, redox

Keywords

Fe oxides|Solid-phase speciation|C stabilization|Mössbauer spectroscopy

Variables

iron|ferric ion|ferrous ion

Variables ODM2

Iron




TEMPORAL

Date Start

2016-05-15

Date End

2018-04-21




SPATIAL

Field Areas

Northeastern Puerto Rico and the Luquillo Mountains

Location

Luquillo Mountains

North latitude

18.361

South latitude

18.2267

West longitude

-65.8514

East longitude

-65.6921




REFERENCE

Citation

Elizabeth K.Coward, AaronThompson, Alain F.Plante (2018): Contrasting Fe speciation in two humid forest soils: Insight into organomineral associations in redox-active environments. Geochimica et Cosmochimica Acta. DOI: 10.1016/j.gca.2018.07.007

Publications of this data

Elizabeth K.Coward, AaronThompson, Alain F.Plante (2018). Contrasting Fe speciation in two humid forest soils: Insight into organomineral associations in redox-active environments. Geochimica et Cosmochimica Acta http://dx.doi.org/10.1016/j.gca.2018.07.007

CZO ID

7169



Additional Metadata

Name Value
czos Luquillo
czo_id 7169
citation Elizabeth K.Coward, AaronThompson, Alain F.Plante (2018): Contrasting Fe speciation in two humid forest soils: Insight into organomineral associations in redox-active environments. Geochimica et Cosmochimica Acta. DOI: 10.1016/j.gca.2018.07.007
keywords Fe oxides, Solid-phase speciation, C stabilization, Mössbauer spectroscopy
subtitle Contrasting Fe speciation in two humid forest soils: Insight into organomineral complexation in redox-active environments
variables iron, ferric ion, ferrous ion
disciplines Biogeochemistry, Soil Science / Pedology

References

Related Resources

The content of this resource serves as the data for: Elizabeth K.Coward, AaronThompson, Alain F.Plante (2018). Contrasting Fe speciation in two humid forest soils: Insight into organomineral associations in redox-active environments. Geochimica et Cosmochimica Acta http://dx.doi.org/10.1016/j.gca.2018.07.007

How to Cite

Coward, E. K., A. Thompson, A. F. Plante (2019). LCZO -- Soil Redox Potential, Soil Biogeochemistry -- Fe speciation, redox -- Luquillo Mountains -- (2016-2018), HydroShare, http://www.hydroshare.org/resource/e6d7f6c11aa34662bdc30225bf35ae6e

This resource is shared under the Creative Commons Attribution CC BY.

 http://creativecommons.org/licenses/by/4.0/
CC-BY

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