Ce4Ag3Ge4O(0.5)--chains of oxygen-centered [OCe2Ce(2/2)] tetrahedra embedded in a [CeAg3Ge4] intermetallic matrix.
The oxidation of an intermetallic phase under high-pressure/high-temperature conditions led to the synthesis of Ce4Ag3Ge4O(0.5) exhibiting [OCe2Ce(2/2] tetrahedral chains, in which the oxygen atoms statistically occupy the tetrahedral centres. Starting from a 1:1:1 CeAgGe precursor (NdPtSb type), a multianvil high-pressure/high-temperature experiment at 11.5 GPa and 1250-1300 °C revealed Ce4Ag3Ge4O(0.5), crystallizing in the space group Pnma with the following lattice parameters: a = 2087.3(4), b = 439.9(1), and c = 1113.8(2) pm. Magnetic measurements showed Curie-Weiss behavior above 100 K with an experimental magnetic moment of 2.42 µB per Ce atom, close to the value for the free Ce(3+) ion, clearly indicating trivalent cerium in Ce4Ag3Ge4O(0.5). Full potential GGA+U band structure calculations resulted in metallic properties and a magnetic ground state with one unpaired 4f-electron per cerium in agreement with the experiments.
New quaternary arsenide oxides with square planar coordination of gold(I) - structure, (197)Au Mössbauer spectroscopic, XANES and XPS characterization of Nd10Au3As8O10 and Sm10Au3As8O10.
The quaternary gold(I) arsenide oxides Nd10Au3As8O10 and Sm10Au3As8O10 were synthesized in sealed quartz ampoules from the rare earth (RE) elements, their appropriate sesquioxides, arsenic, arsenic(III) oxide and finely dispersed gold at maximum annealing temperatures of 1223 K. Both structures were refined from X-ray single crystal diffractometer data at room temperature and at 90 K. Nd10Au3As8O10 and Sm10Au3As8O10 crystallize with a new structure type that derives from the BaAl4 structure through distortions and formation of ordered vacancies. The structures consist of stacked polycationic [RE10O10](10+) layers with oxygen in tetrahedral rare earth coordination and polyanionic [Au(I)3(As2)4](10-) layers with gold in square planar or rectangular planar coordination of four arsenic dumbbells (255 pm As1-As2). In contrast to the well known ionic rare earth oxide layers, the gold arsenide layers rather show covalent bonding and account for the metallic nature of these two new arsenide oxides. This is confirmed by electronic structure calculations and resistivity measurements. The oxidation state of gold was investigated by (197)Au Mössbauer, X-ray absorption near edge structure (XANES) and photoelectron (XPS) spectroscopy. Due to missing comparative gold arsenide compounds, the monovalent gold phosphide oxides RE2AuP2O were measured for comparison. The XANES measurements additionally comprise monovalent gold arsenides REAuAs2. The XPS study contains BaAuAs as reference compound instead. Combination of all data clearly indicates Au(I), which was not observed in square planar coordination up to now. Temperature dependent magnetic susceptibility data show Curie-Weiss paramagnetism for Nd10Au3As8O10 and no magnetic ordering down to 2.5 K. Sm10Au3As8O10 shows the typical Van Vleck type paramagnetism for samarium compounds along with a transition to an antiferromagnetically ordered state at TN = 8.6 K.
Experimental study of water fluxes in a residential area: 2. Road infiltration, runoff and evaporation
Lack of accurate data has led some hydrologists and city planners to assume that urban infiltration is zero and runoff is 100% of the rainfall. These assumptions lead to an over estimation of road runoff volume and an underestimation of direct recharge to groundwater, which is already rising under some UK cities. This study investigates infiltration and runoff processes and quantifies the percentage of rainfall that contributes to storm drainage, and that which infiltrates through different types of road surface. Access tubes were installed for measuring soil water content using a neutron probe in three car parks, a road and a grass site at the Centre for Ecology and Hydrology, Crowmarsh Gifford, Wallingford. Storm drainage was recorded at the exit of the Thamesmead Estate in Crowmarsh Gifford, just before the drain joins the River Thames at Wallingford. Rainfall and water table depth were also recorded. Weekly measurements of soil moisture content indicated that the top 40 cm layer is not influenced by water‐table fluctuations and, therefore, positive changes in soil moisture could be attributed to infiltration of rainfall through the surface. Depending on the nature of the surface, subsurface layers, level of traffic, etc., between 6 and 9% of rainfall was found to infiltrate through the road surfaces studied. The storm drainage generated by road runoff revealed a flow pattern similar to that of the receiving watercourse (River Thames) and increased with the increase of infiltration and soil water content below the road surface. The ratio of runoff to rainfall was 0·7, 0·9 and 0·5 for annual, winter (October–March) and summer (April–September) respectively. As the results of the infiltration indicated that 6 to 9% of annual rainfall infiltrates through the road surface, this means that evaporation represents, 21–24% of annual rainfall, with more evaporation taking place during summer than winter. Copyright © 2003 John Wiley & Sons, Ltd.