Stabilities of thiomolybdate complexes of iron; implications for retention of essential trace elements (Fe, Cu, Mo) in sulfidic waters.

In aquatic ecosystems, availabilities of Fe, Mo and Cu potentially limit rates of critical biological processes, including nitrogen fixation, nitrate assimilation and N2O decomposition. During long periods in Earth's history when large parts of the ocean were sulfidic, what prevented these elements' quantitative loss from marine habitats as insoluble sulfide phases? They must have been retained by formation of soluble complexes. Identities of the key ligands are poorly known but probably include thioanions. Here, the first determinations of stability constants for Fe(2+)-[MoS4](2-) complexes in aqueous solution are reported based on measurements of pyrrhotite (hexagonal FeS) solubility under mildly alkaline conditions. Two linear complexes, [FeO(OH)MoS4](3-) and [(Fe2S2)(MoS4)2](4-), best explain the observed solubility variations. Complexes that would be consistent with cuboid cluster structures were less successful, implying that such clusters probably are minor or absent in aqueous solution under the conditions studied. The new data, together with prior data on stabilities of Cu(+)-[MoS4](2-) complexes, are used to explore computationally how competition of Fe(2+) and Cu(+) for [MoS4](2-), as well as competition of [MoS4](2-) and HS(-) for both metals would be resolved in solutions representative of sulfidic natural waters. Thiomolybdate complexes will be most important at sulfide concentrations near the [MoO4](2-)-[MoS4](2-) equivalence point. At lower sulfide concentrations, thiomolybdates are insufficiently stable to be competitive ligands in natural waters and at higher sulfide concentrations HS(-) ligands out-compete thiomolybdates.

Molybdenum scavenging by iron monosulfide.

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.