The Future of the Clean Development Mechanism. Note on the report “A Call to Action” of the High-Level Panel on CDM Policy Dialogue. CEPS Special Report No. 71, 20 November 2012

The clean development mechanism (CDM) has been through a long and complex growing process since it was approved as part of the Kyoto Protocol. It was designed within the framework of the UNFCCC and the Kyoto Protocol, and reflected the political and economic realities of that time. To ensure its continued effectiveness in contributing to future global climate action and to reflect on how best to position the CDM to respond to future challenges, a high-level panel (HLP) was formed at the Durban climate change conference in 2011. Following extensive consultations, the panel published its report in September 2012. Through this Special Report, the CEPS Carbon Market Forum offers its reflections on findings and recommendations of the HLP, as well as, by extension, its own views on the future of the CDM. In the context of the latter, it explores the following questions: Is there a need for an instrument such as the CDM in the future? What ‘demand’ can it fill? In the roles identified under the first question, what can be done to adapt it and also continue to increase its efficacy?

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.

Layer-by-layer electrostatic entrapment of protein molecules on superparamagnetic nanoparticle: new strategy to enhance adsorption capacity and maintain biological activity

There is a recent interest to use inorganic-based magnetic nanoparticles as a vehicle to carry biomolecules for various biophysical applications, but direct attachment of the molecules is known to alter their conformation leading to attenuation in activity. In addition, surface immobilization has been limited to monolayer coverage. It is shown that alternate depositions of negatively charged protein molecules, typically bovine serum albumin (BSA) with a positively charged aminocarbohydrate template such as glycol chitosan (GC) on magnetic iron oxide nanoparticle surface as a colloid, are carried out under pH 7.4. Circular dichroism (CD) clearly reveals that the secondary structure of the entrapped BSA sequential depositions in this manner remains totally unaltered which is in sharp contrast to previous attempts. Probing the binding properties of the entrapped BSA using small molecules (Site I and Site II drug compounds) confirms for the first time the full retention of its biological activity as compared with native BSA, which also implies the ready accessibility of the entrapped protein molecules through the porous overlayers. This work clearly suggests a new method to immobilize and store protein molecules beyond monolayer adsorption on a magnetic nanoparticle surface without much structural alteration. This may find applications in magnetic recoverable enzymes or protein delivery.

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 1 - the water column

This paper investigates phosphorus (P) transport and transformation dynamics in two contrasting sub-catchments of the River Kennel, England. Samples were collected daily under baseflow and hourly under stormflow conditions using autosamplers for 2 years and analysed for a range of determinands (full P fractionation, suspended sediment (SS), cations, pH, alkalinity, temperature and oxygen). Concentrations of SRP, SUP, PP and SS were higher in the flashy River Enborne (means of 0.186, 0.071, 0.101 and 34 mg l(-1), respectively) than the groundwater-fed River Lambourn (0.079, 0.057, 0.028 and 9 mg l(-1), respectively). A seasonal trend in the daily P dataset was evident, with lower concentrations during intermediate flows and the spring (caused by a dilution effect and macrophyte uptake) than during baseflow conditions. However, in the hourly P dataset, highest concentrations were observed during storm events in the autumn and winter (reflecting higher scour with increased capacity to entrain particles). Storm events were more significant in contributing to the total P load in the River Enborne than the River Lambourn, especially during August to October, when dry antecedent conditions were observed in the catchment. Re-suspension of P-rich sediment that accumulated within the channel during summer low flows might account for these observations. It is suggested that a P-calcite co-precipitation mechanism was operating during summer in the River Lambourn, while adsorption by metal oxyhydroxide groups was an important mechanism controlling P fractionation in the River Enborne. The influence of flow conditions and channel storage/release mechanisms on P dynamics in these two lowland rivers is assessed. (C) 2004 Elsevier B.V. All rights reserved.

Adsorption of water vapor by bare soil in an olive grove in southern Spain

Data for water vapor adsorption and evaporation are presented for a bare soil (sandy loam, clay content 15%) in a southern Spanish olive grove. Water losses and gains were measured using eight high-precision minilysimeters, placed around an olive tree, which had been irrigated until the soil reached field capacity (similar to 0.22 m(3) m(-3)). They were subsequently left to dry for 10 days. A pair of lysimeters was situated at each of the main points of the compass (N, E, S, W), at a distance of 1 m (the inner set of lysimeters; ILS) and 2 m (the outer set of lysimeters; OLS), respectively, from the tree trunk. Distinct periods of moisture loss (evaporation) and moisture gain (vapor adsorption) could be distinguished for each day. Vapor adsorption often started just after noon and generally lasted until the (early) evening. Values of up to 0.7 mm of adsorbed water per day were measured. Adsorption was generally largest for the OLS (up to 100% more on a daily basis), and increased during the dry down. This was mainly the result of lower OLS surface soil moisture contents (period-average absolute difference similar to 0.005 m(3) m(-3)), as illustrated using various analyses employing a set of micrometeorological equations describing the exchange of water vapor between bare soil and the atmosphere. These analyses also showed that the amount of water vapor adsorbed by soils is very sensitive to changes in atmospheric forcing and surface variables. The use of empirical equations to estimate vapor adsorption is therefore not recommended.

Polymer-drug conjugates for combination anticancer therapy: investigating the mechanism of action.

We developed a family of polymer-drug conjugates carrying the combination of the anticancer agent epirubicin (EPI) and nitric oxide (NO). EPI-PEG-(NO)8, carrying the highest content of NO, displayed greater activity in Caco-2 cells while it decreased toxicity against endothelium cells and cardiomyocytes with respect to free EPI. FACS and confocal microscopy confirmed conjugates internalization. Light scattering showed formation of micelle whose size correlated with internalization rate. EPI-PEG-(NO)8 showed increased bioavailability in mice compared to free EPI.

The formation mechanism of the Bonin high in August

The Bonin high is a subtropical anticyclone that is predominant near Japan in the summer. This anticyclone is associated with an equivalent-barotropic structure, often extending throughout the entire troposphere. Although the equivalent-barotropic structure of the Bonin high has been known for years among synopticians because of its importance to the summer climate in east Asia, there are few dynamical explanations for such a structure. The present paper attempts to provide a formation mechanism for the deep ridge near Japan. We propose a new hypothesis that this equivalent-barotropic ridge near Japan is formed as a result of the propagation of stationary Rossby waves along the Asian jet in the upper troposphere (‘the Silk Road pattern’). First, the monthly mean climatology is examined in order to demonstrate this hypothesis. It is shown that the enhanced Asian jet in August is favourable for the propagation of stationary Rossby waves and that the regions of descent over the eastern Mediterranean Sea and the Aral Sea act as two major wave sources. Second, a primitive-equation model is used to simulate the climatology of August. The model successfully simulates the Bonin high with an equivalent-barotropic structure. The upper-tropospheric ridge is found to be enhanced by a height anomaly of more than 80 m at 200 hPa, when a wave packet arrives. Sensitivity experiments are conducted to show that the removal of the diabatic cooling over the Asian jet suppresses the Silk Road pattern and formation of an equivalent-barotropic ridge near Japan, while the removal of the diabatic heating in the western Pacific does not. Copyright © 2003 Royal Meteorological Society

The propagation mechanism of a vortex on the β plane

The propagation velocity and propagation mechanism for vortices on a β plane are determined for a reduced-gravity model by integrating the momentum equations over the β plane. Isolated vortices, vortices in a background current, and initial vortex propagation from rest are studied. The propagation mechanism for isolated anticyclones as well as cyclones, which has been lacking up to now, is presented. It is shown that, to first order, the vortex moves to generate a Coriolis force on the mass anomaly of the vortex to compensate for the force on the vortex due to the variation of the Coriolis parameter. Only the mass anomaly of the vortex is of importance, because the Coriolis force due to the motion of the bulk of the layer moving with the vortex is almost fully compensated by the Coriolis force on the motion of the exterior flow. Because the mass anomaly of a cyclone is negative the force and acceleration have opposite sign. The role of dipolar structures in steadily moving vortices is discussed, and it is shown that their overall structure is fixed by the steady westward motion of the mass anomaly. Furthermore, it is shown that reduced-gravity vortices are not advected with a background flow. The reason for this behavior is that the background flow changes the ambient vorticity gradient such that the vortex obtains an extra self-propagation term that exactly cancels the advection by the background flow. Last, it is shown that a vortex initially at rest will accelerate equatorward first, after which a westward motion is generated. This result is independent of the sign of the vortex.

CISK or WISHE as the mechanism for tropical cyclone intensification

Examination of conditional instability of the second kind (CISK) and wind-induced surface heat exchange (WISHE), two proposed mechanisms for tropical cyclone and polar low intensification, suggests that the sensitivity of the intensification rate of these disturbances to surface properties, such as surface friction and moisture supply, will be different for the two mechanisms. These sensitivities were examined by perturbing the surface characteristics in a numerical model with explicit convection. The intensification rate was found to have a strong positive dependence on the heat and moisture transfer coefficients, while remaining largely insensitive to the frictional drag coefficient. CISK does not predict the observed dependence of vortex intensification rate on the heat and moisture transfer coefficients, nor the insensitivity to the frictional drag coefficient since it anticipates that intensification rate is controlled by frictional convergence in the boundary layer. Since neither conditional instability nor boundary moisture content showed any significant sensitivity to the transfer coefficients, this is true of CISK using both the convective closures of Ooyama and of Charney and Eliassen. In comparison, the WISHE intensification mechanism does predict the observed increase in intensification rate with heat and moisture transfer coefficients, while not anticipating a direct influence from surface friction.

Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.