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Biogeochemical controls on iron speciation and cycling across upland to shoreline gradients in freshwater and estuarine coastal soils (Lake Erie and Chesapeake Bay, United States)

Journal Article · · Science of the Total Environment
 [1];  [2];  [3];  [4];  [3];  [4];  [4];  [4];  [5];  [3];  [6];  [7];  [4];  [8];  [3];  [7];  [5];  [6];  [6];  [3]
  1. Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Manchester (United Kingdom). Radioactive Waste Disposal and Environmental Remediation National Nuclear User Facility
  2. Argonne National Laboratory (ANL), Argonne, IL (United States); Bulgarian Academy of Sciences, Sofia (Bulgaria)
  3. Argonne National Laboratory (ANL), Argonne, IL (United States)
  4. Univ. of Toledo, OH (United States)
  5. Smithsonian Environmental Research Center, Edgewater, MD (United States)
  6. Univ. of Toledo, OH (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  7. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  8. Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Coastal environments are dynamic interfaces that mediate carbon and nutrient exchanges between terrestrial landscapes and open waters, and understanding the biogeochemical factors controlling these exchanges, particularly iron (Fe) redox transformations, is crucial for predicting coastal ecosystem functions. Here, we investigated the mechanisms controlling Fe speciation changes across upland-to-shoreline gradients in freshwater and estuarine soils using Fe K-edge X-ray absorption spectroscopy, solid and porewater composition analysis, and 16S rRNA sequencing analysis. We show that Fe transformations depend primarily on inundation patterns. In unsaturated uplands, Fe occurs as Fe(III) oxyhydroxides, mainly goethite (9–35 %), Fe(II,III)-phyllosilicates (39–89 %), and Fe(III)-organic species (0–61 %). Soils influenced by estuarine waters exhibit porewater sulfide concentrations reaching up to 221 μM, Fe- and S-cycling bacteria, and up to 81 % pyrite (FeS2), indicating that sulfur-driven redox dynamics control Fe transformations. In lacustrine wetlands, Fe(III) reduction is indicated by porewater Fe(II) concentrations increasing to 1.0–2.1 mM, and ~10–15 % of Fe as Fe(II,III)-(hydr)oxides (green rust), vivianite (Fe3(PO4)2·8H2O), and/or adsorbed Fe(II) species. EXAFS data also indicate reduction of structural Fe(III) to Fe(II) in phyllosilicates. The presence of Fe- and S-cycling bacteria, as well as sulfide (0–10 μM), suggests that Fe-cycling is microbially driven and potentially coupled with cryptic S-cycling. Fe(II) oxidation was indicated above/near the water table by the presence of Fe(III) oxyhydroxides (ferrihydrite, lepidocrocite). Furthermore, negligible Fe(III) or sulfate reduction was observed at some water-saturated sites located at the upland-wetland transition, likely due to oxic (sub-)surface water inputs. Overall, our results highlight the importance of considering both Fe-speciation and hydro-biogeochemical dynamics when predicting Fe-cycling at coastal interfaces.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-76RL01830; AC02-06CH11357
OSTI ID:
2573932
Alternate ID(s):
OSTI ID: 2584174
Report Number(s):
PNNL-SA--214082
Journal Information:
Science of the Total Environment, Journal Name: Science of the Total Environment Vol. 991; ISSN 0048-9697
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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