Adsorption, orientation and thermal decomposition of copper(II) hexafluoroacetylacetonate on rutile TiO2(110)

We have investigated the adsorption and thermal decomposition of copper hexafluoroacetylacetonate (Cu-11(hfaC)(2)) on single crystal rutile TiO2(110). Low energy electron diffraction shows that room temperature saturation coverage of the Cu-II(hfac)(2) adsorbate forms an ordered (2 x 1) over-layer. X-ray and ultra-violet photoemission spectroscopy of the saturated surface were recorded as the sample was annealed in a sequential manner to reveal decomposition pathways. The results show that the molecule dissociatively adsorbs by detachment of one of the two ligands to form hfac and Cu-1(hfac) which chemisorb to the substrate at 298 K. These ligands only begin to decompose once the surface temperature exceeds 473 K where Cu core level shifts indicate metallisation. This reduction from Cu(I) to Cu(0) takes place in the absence of an external reducing agent and without disproportionation and is accompanied by the onset of decomposition of the hfac ligands. Finally, C K-edge near edge X-ray absorption fine structure experiments indicate that both the ligands adsorb aligned in the < 001 > direction and we propose a model in which the hfac ligands adsorb on the 5-fold coordinated Ti atoms and the Cu-1(hfac) moiety attaches to the bridging O atoms in a square planar geometry. The calculated tilt angle for these combined geometries is approximately 10 degrees to the surface normal.

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50 t ha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50 t ha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50 t ha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability. (c) 2007 Elsevier Ltd. All rights reserved.

Changes in the extent of glaciers in the Eastern Terskey Alatoo, the Central Tien-Shan, in response to climatic fluctuations in between the end of the 19th and the beginning of the 21st century

Changes in the extent of glaciers and rates of glacier termini retreat in the eastern Terskey-Alatoo Range, the Tien Shan Mountains, Central Asia have been evaluated using the remote sensing techniques. Changes in the extent of 335 glaciers between the end of the Little Ice Age (LIA; mid-19th century), 1990 and 2003 have been estimated through the delineation of glacier outlines and the LIA moraine positions on the Landsat TM and ASTER imagery for 1990 and 2003 respectively. By 2003, the glacier surface area had decreased by 19% of the LIA value, which constitutes a 76 km(2) reduction in glacier surface area. Mapping of 109 glaciers using the 1965 1:25,000 maps revealed that glacier surface area decreased by 12.6% of the 1965 value between 1965 and 2003. Detailed mapping of 10 glaciers using historical maps and aerial photographs from the 1943-1977 period, has enabled glacier extent variations over the 20th century to be identified with a higher temporal resolution. Glacial retreat was slow in the early 20th century but increased considerably between 1943 and 1956 and then again after 1977. The post-1990 period has been marked by the most rapid glacier retreat since the end of the LIA. The observed changes in the extent of glaciers are in line with the observed climatic warming. The regional weather stations have revealed a strong climatic warming during the ablation season since the 1950s at a rate of 0.02-0.03 degrees Ca-1. At the higher elevations in the study area represented by the Tien Shan meteorological station, the summer warming was accompanied by negative anomalies in annual precipitation in the 1990s enhancing glacier retreat. However, trends in precipitation in the post-1997 period cannot be evaluated due to the change in observational practices at this station. Neither station in the study area exhibits significant long-term trends in precipitation. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Morphology, biomass and nutrient status of fine roots of Scots pine (Pinus sylvestris) as influenced by seasonal fluctuations in soil moisture and soil solution chemistry

A field monitoring study was carried out to follow the changes of fine root morphology, biomass and nutrient status in relation to seasonal changes in soil solution chemistry and moisture regime in a mature Scots pine stand on acid soil. Seasonal and yearly fluctuations in soil moisture and soil solution chemistry have been observed. Changes in soil moisture accounted for some of the changes in the soil solution chemistry. The results showed that when natural acidification in the soil occurs with low pH (3.5-4.2) and high aluminium concentration in the soil solution (> 3-10 mg l(-1)), fine root longevity and distribution could be affected. However, fine root growth of Scots pine may not be negatively influenced by adverse soil chemical conditions if soil moisture is not a limiting factor for root growth. In contrast, dry soil conditions increase Scots pine susceptibility to soil acidification and this could significantly reduce fine root growth and increase root mortality. It is therefore important to study seasonal fluctuations of the environmental variables when investigating and modelling cause-effect relationships.