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interactions between phosphate and various Fe (oxyhydr)oxides are poorly constrained in natural systems. An in-situ incubation experiment was conducted to explore Fe (oxyhydr)oxide transformation and effects on phosphate sorption in soils with contrasting saturation and redox conditions. Synthetic Fe (oxyhydr)oxides (ferrihydrite, goethite and hematite) were coated onto quartz sand and either pre-sorbed with phosphate or left phosphate-free. The oxide-coated sands were mixed with natural organic matter, enclosed in mesh bags, and buried in and around a vernal pond for up to 12 weeks. Redox conditions were stable and oxic in the upland soils surrounding the vernal pond but largely shifted from Fe reducing to Fe oxidizing in the lowland soils within the vernal pond as it dried during the summer. Iron (oxyhydr)oxides lost more Fe (− 41% ± 10%) and P (− 43 ± 11%) when incubated in the redox-dynamic lowlands compared to the uplands (− 18% ± 5% Fe and − 24 ± 8% P). Averaged across both uplands and lowlands, Fe losses from crystalline goethite and hematite (− 38% ± 6%) were unexpectedly higher than losses from short range ordered ferrihydrite (− 12% ± 10%). We attribute losses of Fe and associated P from goethite and hematite to colloid detachment and dispersion but losses from ferrihydrite to reductive dissolution. Iron losses were partially offset by retention of solubilized Fe as organic-bound Fe(III). Iron (oxyhydr)oxides that persisted during the incubation retained or even gained P, indicating low amounts of phosphate sorption from solution. These results demonstrate that hydrologic variability and Fe (oxyhydr)oxide mineralogy impact Fe mobilization pathways that may regulate phosphate bioavailability.
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The primacy of temporal dynamics in driving spatial self-organization of soil iron redox patterns
This study investigates mechanisms that generate regularly spaced iron-rich bands in upland soils. These striking features appear in soils worldwide, but beyond a generalized association with changing redox, their genesis is yet to be explained. Upland soils exhibit significant redox fluctuations driven by rainfall, groundwater changes, or irrigation. Pattern formation in such systems provides an opportunity to investigate the temporal aspects of spatial self-organization, which have been heretofore understudied. By comparing multiple alternative mechanisms, we found that regular iron banding in upland soils is explained by coupling two sets of scale-dependent feedbacks, the general principle of Turing morphogenesis. First, clay dispersion and coagulation in iron redox fluctuations amplify soil Fe(III) aggregation and crystal growth to a level that negatively affects root growth. Second, the activation of this negative root response to highly crystalline Fe(III) leads to the formation of rhythmic iron bands. In forming iron bands, environmental variability plays a critical role. It creates alternating anoxic and oxic conditions for required pattern-forming processes to occur in distinctly separated times and determines durations of anoxic and oxic episodes, thereby controlling relative rates of processes accompanying oxidation and reduction reactions. As Turing morphogenesis requires ratios of certain process rates to be within a specific range, environmental variability thus modifies the likelihood that pattern formation will occur. Projected changes of climatic regime could significantly alter many spatially self-organized systems, as well as the ecological functioning associated with the striking patterns they present. This temporal dimension of pattern formation merits close attention in the future.
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- Award ID(s):
- 2320296
- PAR ID:
- 10539287
- Publisher / Repository:
- Proceedings of the National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 120
- Issue:
- 51
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.2313487120
