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.

Integrating methods for developing sustainability indicators that can facilitate learning and action

Bossel's (2001) systems-based approach for deriving comprehensive indicator sets provides one of the most holistic frameworks for developing sustainability indicators. It ensures that indicators cover all important aspects of system viability, performance, and sustainability, and recognizes that a system cannot be assessed in isolation from the systems upon which it depends and which in turn depend upon it. In this reply, we show how Bossel's approach is part of a wider convergence toward integrating participatory and reductionist approaches to measure progress toward sustainable development. However, we also show that further integration of these approaches may be able to improve the accuracy and reliability of indicators to better stimulate community learning and action. Only through active community involvement can indicators facilitate progress toward sustainable development goals. To engage communities effectively in the application of indicators, these communities must be actively involved in developing, and even in proposing, indicators. The accuracy, reliability, and sensitivity of the indicators derived from local communities can be ensured through an iterative process of empirical and community evaluation. Communities are unlikely to invest in measuring sustainability indicators unless monitoring provides immediate and clear benefits. However, in the context of goals, targets, and/or baselines, sustainability indicators can more effectively contribute to a process of development that matches local priorities and engages the interests of local people.

Toward an integrated seasonal forecasting system for South America

This study proposes an objective integrated seasonal forecasting system for producing well-calibrated probabilistic rainfall forecasts for South America. The proposed system has two components: ( i) an empirical model that uses Pacific and Atlantic sea surface temperature anomalies as predictors for rainfall and ( ii) a multimodel system composed of three European coupled ocean - atmosphere models. Three-month lead austral summer rainfall predictions produced by the components of the system are integrated ( i. e., combined and calibrated) using a Bayesian forecast assimilation procedure. The skill of empirical, coupled multimodel, and integrated forecasts obtained with forecast assimilation is assessed and compared. The simple coupled multimodel ensemble has a comparable level of skill to that obtained using a simplified empirical approach. As for most regions of the globe, seasonal forecast skill for South America is low. However, when empirical and coupled multimodel predictions are combined and calibrated using forecast assimilation, more skillful integrated forecasts are obtained than with either empirical or coupled multimodel predictions alone. Both the reliability and resolution of the forecasts have been improved by forecast assimilation in several regions of South America. The Tropics and the area of southern Brazil, Uruguay, Paraguay, and northern Argentina have been found to be the two most predictable regions of South America during the austral summer. Skillful rainfall forecasts are generally only possible during El Nino or La Nina years rather than in neutral years.