title: Molybdenum scavenging by iron monosulfide.
abstract: Molybdenum profiles in dated sediment cores provide useful historical information about anoxia in anthropogenically impacted natural waters but would be of greater service if Mo fixation mechanisms were better understood. Here, we explore Mo scavenging by precipitated FeS in a model system consisting of an FeIII-bearing kaolinite (KGa-1B) dispersed in NaHS solutions. Test solutions contain 18 microM thiomolybdates (mainly MoOS3(2-)). Optically measuring dissolved polysulfides monitors the rate of FeS production from FeIII minerals. Even though the exposed clay surface area is large (450 m2/L), the clay itself sorbs little Mo at pH 8.6. As FeS forms, Mo is taken up in initial Mo/Fe mole ratios of 0.04-0.06, irrespective of HS- concentration (4-40 mM range). After about a day, Mo expulsion from the solids begins, accompanied by net polysulfide consumption. These changes reflect recrystallization of amorphous FeS to more ordered products such as greigite. FeS captures some MoO4(2-) but captures thiomolybdates more effectively. Kaolinite accelerates conversion of MoOS3(2-) to MoS4(2-), as predicted previously, and thiomolybdates facilitate reduction of FeIII minerals in the clay compared to Mo-free solutions. FeS is a potentially effective, transient scavenging agent for Mo in sulfidic environments, although FeS2 and organic matter appear to be the ultimate sedimentary hosts.
authors.affiliation: Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA. gh17@umail.umd.edu
authors.forename: George R
authors.initials: GR
authors.lastname: Helz
authors.forename: Trent P
authors.initials: TP
authors.lastname: Vorlicek
authors.forename: Mani D
authors.initials: MD
authors.lastname: Kahn
mesh_terms: D000538:Aluminum Silicates / Q000737:chemistry; D011232:Chemical Precipitation; D000077215:Clay; D005296:Ferrous Compounds / Q000737:chemistry*; D019015:Geologic Sediments / Q000737:chemistry; D007616:Kaolin / Q000737:chemistry; D008982:Molybdenum / Q000032:analysis* / Q000737:chemistry*; D055095:Optics and Photonics
chemical_list: D000538:Aluminum Silicates; D005296:Ferrous Compounds; D007616:Kaolin; D008982:Molybdenum; D000077215:Clay; C022597:ferrous sulfide