Consistent Controls on Trace Metal Micronutrient Speciation in Wetland Soils and Stream Sediments

Journal Article · Thu Oct 28 00:00:00 EDT 2021 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2021.10.017· OSTI ID:1830769

Yan, Jinshu ^[1]; Sharma, Neha ^[1]; Flynn, Elaine D. ^[1]; Giammar, Daniel E.  ^[1]; Schwartz, Grace E.  ^[2]; Brooks, Scott C.  ^[2]; Weisenhorn, Pamela ^[3]; Kemner, Kenneth M.  ^[3]; O'Loughlin, Edward J.  ^[3]; Kaplan, Daniel I. ^[4]; Catalano, Jeffrey G.  ^[1]

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1. Washington Univ., St. Louis, MO (United States)
2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
3. Argonne National Lab. (ANL), Argonne, IL (United States)
4. Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

Trace metal are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, but low availability of these elements may inhibit anaerobic element cycling and transformations. Solid-phase speciation is likely a critical control on trace metal availability but has seen limited study in anoxic systems having concentrations similar to geological background levels, where metal limitations may be most prevalent. We have investigated trace metal concentrations and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed. These systems displayed low solid-phase trace metal concentrations, generally at or below geological background levels, which generally followed the trend Zn > Cu ≈ Ni > Co and showed no correlation with major element compositions. All soils and sediments were dominated by quartz but varied in clay mineralogy as well as the organic matter, total sulfur, and total iron contents. X-ray absorption near-edge structure (XANES) spectroscopy shows that sulfur speciation in both wetlands is dominated by organic sulfur. Elemental sulfur and iron sulfides together made up <25% of the sulfur in the wetland soils, but the distribution between inorganic and organic forms was reversed in the stream sediments. Ferrous and ferric iron in clay minerals were common species identified by both XANES and extended X-ray absorption fine structure (EXAFS) spectroscopies at all sites. Iron(III) oxides were substantial components in all but the marsh wetland soils. Quantitative analysis of copper, nickel, and zinc XANES spectra revealed similar metal speciation across all sites. Copper speciation was dominated by sulfides, adsorbed species, and minor amounts of copper bound to organic matter; no metallic copper was detected. Nickel speciation also varied little and was dominated by nickel in clay mineral octahedral sheets and nickel sulfide, with adsorbed species also present. Zinc speciation was slightly more varied, with the marsh wetland soils and stream bed sediments containing adsorbed species, zinc associated with clay mineral structures, and zinc bound to reduced sulfur groups on organic matter, whereas the riparian wetland soils lacked clay-associated zinc but contained zinc sulfide. Trace metals bound to reduced sulfur occurred at every site, with a greater sulfur-bound fraction for copper. The fractional abundance of sulfur-bound species showed no relationship with soil or sediment total sulfur content, which varied by two orders of magnitude. More broadly, the observations in this study suggest that trace metal speciation in freshwater wetland soils and stream sediments is consistently dominated by a small set of recurring components which are distinct for each metal. Furthermore, this may represent a general geochemical phenomenon in anoxic soils and sediments containing trace metals at background concentrations (as low as 3 µg g^-1) that was not predicted from systems that are contaminated with or naturally-enriched in copper, nickel, or zinc.

• Research Organization: Washington Univ., St. Louis, MO (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Biological and Environmental Research (BER)
• Contributing Organization: SLAC National Accelerator Lab (SLAC); Argonne National Lab. (ANL)
• Grant/Contract Number: SC0019422; AC02-06CH11357; AC09-96SR18500; AC02-76SF00515; AC05-00OR22725
• OSTI ID: 1830769
• Alternate ID(s): OSTI ID: 1845701; OSTI ID: 1856356; OSTI ID: 1868720; OSTI ID: 1872857
• Journal Information: Geochimica et Cosmochimica Acta, Vol. 317; Related Information: Yan J ; Sharma N ; Flynn E ; Giammar D ; Schwartz G ; Brooks S ; Weisenhorn P ; Kemner K ; O'Loughlin E ; Kaplan D ; Catalano J (2021): Soil and Water Chemistry and Trace Metal Extractability and Speciation in Wetland Soils from Illinois and South Carolina and Stream Sediments from Tennessee. Trace Metal Dynamics and Limitations on Biogeochemical Cycling in Wetland Soils and Hyporheic Zones, ESS-DIVE repository. Dataset. doi:10.15485/1773008 accessed via https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1773008 on 2021-11-17; ISSN 0016-7037
• Publisher: Elsevier; The Geochemical Society; The Meteoritical Society
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
58 GEOSCIENCES
trace metals
wetlands
stream sediments
speciation
XANES
copper
nickel
zinc
methanogenesis