Spatial variation in pyritization of trace metals in salt-marsh soils

In the present study, the pyritization of trace metals was studied in 12soils from 3 salt marshes in the Ría of Ortigueira (NW Spain). Theconcentrations of trace metals in the pyrite fraction were related tophysicochemical conditions, physiographical position in the salt marsh, and thepresence or absence and type of vegetation. Redox conditions in soils from thelow-salt marsh and from the creek bottom were strongly reducing throughout theprofile, and there were higher concentrations of Fe and some trace metals (Cuand Mn) in the pyrite fraction (soluble in HNO₃) than in thereactivefraction (soluble in 1N HCl). In contrast, the trace-metal content in pyritefraction in the surface layers of the high-salt marsh was low. In some of thesoils, there was a significant increase in the pyrite content below 25cm, and levels of Fe, Mn and Cu incorporated into this fractionwere similar to those in the reactive fraction. The degree of pyritizationvaried greatly among metals in the order: CuFe-1NHCl>dithionite-Fe>NiMn>>Zn>Cr, although when we consideredonly the amorphous forms (ascorbate-Fe) as reactive-Fe, the order was:ascorbate-Fe>>Cu>NiMn>>Zn>Cr. These differences appearedto be a consequence of the different geochemical behaviour of each metal(mainlyin terms of the thermodynamic stability of sulfides and reaction kinetics),except for Zn. The low concentrations of Zn obtained may have been due to thesolubility of ZnS in 1N HCl, which meant that it was extracted with thereactivefraction. Finally, we observed a direct relationship between DOP and DTMP,whichwas independent of the geochemical behaviour of each metal and of itsconcentration in the soil. Thus, the strong correlation between pyrite-Fe andthe metals associated with this fraction appears to indicate that these metalscoprecipitate with pyrite rather than form metal sulfides.