Global climate forcing on late Miocene establishment of the Pampean aeolian system in South America.

Wind-blown dust from southern South America links the terrestrial, marine, atmospheric, and biological components of Earth's climate system. The Pampas of central Argentina (~33°-39° S) contain a Miocene to Holocene aeolian record that spans an important interval of global cooling. Upper Miocene sediment provenance based on n = 3299 detrital-zircon U-Pb ages is consistent with the provenance of Pleistocene-Holocene deposits, indicating the Pampas are the site of a long-lived fluvial-aeolian system that has been operating since the late Miocene. Here, we show the establishment of aeolian sedimentation in the Pampas coincided with late Miocene cooling. These findings, combined with those from the Chinese Loess Plateau (~33°-39° N) underscore: (1) the role of fluvial transport in the development and maintenance of temporally persistent mid-latitude loess provinces; and (2) a global-climate forcing mechanism behind the establishment of large mid-latitude loess provinces during the late Miocene.

A westerly wind dominated Puna Plateau during deposition of upper Pleistocene loessic sediments in the subtropical Andes, South America.

The Tafí del Valle depression (~27° S) in the eastern Andes of Argentina provides a record of late Pleistocene dust deposition in the subtropics of South America. We present large-n U-Pb geochronology data for detrital zircons from upper Pleistocene loess-paleosol deposits. When compared to regional data, the age spectra from the Tafí del Valle samples are most like the southern Puna Plateau, supporting derivation largely from the west and northwest. This runs counter to hypotheses suggesting these loessic sediments were derived from the low elevation plains to the east or extra-Andean Patagonia. Mapping of linear wind erosion features on the Puna Plateau yield a mean orientation of 125.7° (1 s.d. = 12.4°). These new data and existing records are consistent with a westerly-northwesterly dominated (upper- and lower-level) wind system over the southern Puna Plateau (to at least ~27° S) during periods of high dust accumulation in Tafí del Valle.

Rates of water exchange for two cobalt(II) heteropolyoxotungstate compounds in aqueous solution.

Polyoxometalate ions are used as ligands in water-oxidation processes related to solar energy production. An important step in these reactions is the association and dissociation of water from the catalytic sites, the rates of which are unknown. Here we report the exchange rates of water ligated to Co(II) atoms in two polyoxotungstate sandwich molecules using the (17)O-NMR-based Swift-Connick method. The compounds were the [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) and the larger αßßα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-) ions, each with two water molecules bound trans to one another in a Co(II) sandwich between the tungstate ligands. The clusters, in both solid and solution state, were characterized by a range of methods, including NMR, EPR, FT-IR, UV-Vis, and EXAFS spectroscopy, ESI-MS, single-crystal X-ray crystallography, and potentiometry. For [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) at pH 5.4, we estimate: k(298)=1.5(5)±0.3×10(6) s(-1), ΔH(≠)=39.8±0.4 kJ mol(-1), ΔS(≠)=+7.1±1.2 J mol(-1) K(-1) and ΔV(≠)=5.6 ±1.6 cm(3) mol(-1). For the Wells-Dawson sandwich cluster (αßßα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-)) at pH 5.54, we find: k(298)=1.6(2)±0.3×10(6) s(-1), ΔH(≠)=27.6±0.4 kJ mol(-1) ΔS(≠)=-33±1.3 J mol(-1) K(-1) and ΔV(≠)=2.2±1.4 cm(3) mol(-1) at pH 5.2. The molecules are clearly stable and monospecific in slightly acidic solutions, but dissociate in strongly acidic solutions. This dissociation is detectable by EPR spectroscopy as S=3/2 Co(II) species (such as the [Co(H(2)O)(6)](2+) monomer ion) and by the significant reduction of the Co-Co vector in the XAS spectra.