Chemical fractionation of metals in wetland sediments: Indiana Dunes National Lakeshore.

Tessier-type (1979) sequential extractions for heavy metals (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) were conducted on sediments from two wetland sites, one inundated and the other drained, within the Indiana Dunes National Lakeshore (IDNL), NW Indiana, with the objective of (i) evaluating extraction techniques on organic-rich sediments, (ii) determining the geochemistry and mobility of potentially biotoxic trace metals in a contaminated environment, and (iii) considering the implications of different restoration strategies on the potential for heavy metal remobilization. Long and repeated extractions were needed to effectively degrade the organic-rich sediments (up to 75% of the sediment by mass). Analysis of sulfur fractionation revealed that it was predominantly sequestered along with the organically bound fraction (renamed oxidizable). Metal recovery was good with the sum of the extractant steps typically within 20% of the total metal concentration determined after total microwave digestion. Results showed metal fractionation to be both metal- and site-specific, The oxidizable fraction is dominant for Cu, Cr, and Fe (>65% of the nonresidual fraction for almost all samples) and overall is most important also for Cd and Pb. The iron/manganese oxide fraction is important for Pb, Mn, and Zn, particularly at the drained site. The carbonate bound fraction is relatively insignificant at both sites, except for Cd and Mn, although it is more important at the drained site. The exchangeable fraction is significant in the uppermost sediments at the drained site, particularly for Cd (3-24%), Pb (3-14%), and Zn (36-45%); whereas, for the inundated site, it ranged only from 0 to 1% Zn, with no detectable Cd or Pb. Chromium, Cu, and Fe exist in forms not likely to be remobilized, whereas Cd, Mn, Pb, and Zn are potentially mobile if drained wetland sites are reflooded (and pH and redox potential altered). Simple mass balance calculations illustrate the potential for the removal of approximately 84,375 kg of exchangeable Zn if currently drained sites across the IDNL are reflooded, with concentrations in water draining into Lake Michigan as high as 5 ppm.