Tephra-linked peat humification records from Irish ombrotrophic bogs question nature of solar forcing at 850 cal. yr BC.

This paper investigates evidence for palaeoclimatic changes during the period ca. 1500-500 cal. yr BC through peat humification studies on seven Irish ombrotrophic bogs. The sites are well-correlated by the identification of three mid-first millennium BC tephras, which enable the humification records at specific points in time to be directly compared. Phases of temporarily increased wetness are suggested at ca. 1300-1250 cal. yr BC, ca. 1150-1050 cal. yr BC, ca. 940 cal. yr BC and ca. 740 cal. yr BC. The last of these is confirmed to be synchronous at five sites, suggesting external forcing on a regional scale. The timing of this wet-shift is constrained by two closely dated tephras and is demonstrated to be distinct from the widely reported changes to cooler/wetter conditions associated with a solar minimum at 850-760 cal. yr BC, at which time the Irish sites appear instead to experience drier conditions. The results suggest the possibility of either non-uniform responses to solar forcing in northwest Europe at this time, or the existence of unrelated climate events in the early first millennium BC. The findings caution against the correlation of loosely dated palaeoclimate data if the effects of forcing mechanisms are to be understood.

DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.