Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.

Improved simulation of water vapour and clear-sky radiation using 24 hour forecasts from ERA40

Monthly mean water vapour and clear-sky radiation extracted from the European Centre for Medium Range Weather Forecasts 40-year reanalysis (ERA40) forecasts are assessed using satellite observations and additional reanalysis data. There is a marked improvement in the interannual variability of column-integrated water vapour (CWV) over the oceans when using the 24-hour forecasts compared with the standard 6-hour forecasts products. The spatial distribution of CWV are well simulated by the 6-hour forecasts; using the 24-hour forecasts does not degrade this simulation substantially and in many cases improves on the quality. There is also an improved simulation of clear-sky radiation from the 24-hour forecasts compared with the 6-hour forecasts based on comparison with satellite observations and empirical estimates. Further work is required to assess the quality of water vapour simulation by reanalyses over land regions. Over the oceans, it is recommended that 24-hour forecasts of CWV and clear-sky radiation are used in preference to the standard 6-hour forecast products from ERA40

Monitoring present day changes in water vapour and the radiative energy balance using satellite data, reanalyses and models

A combination of satellite data, reanalysis products and climate models are combined to monitor changes in water vapour, clear-sky radiative cooling of the atmosphere and precipitation over the period 1979-2006. Climate models are able to simulate observed increases in column integrated water vapour (CWV) with surface temperature (Ts) over the ocean. Changes in the observing system lead to spurious variability in water vapour and clear-sky longwave radiation in reanalysis products. Nevertheless all products considered exhibit a robust increase in clear-sky longwave radiative cooling from the atmosphere to the surface; clear-sky longwave radiative cooling of the atmosphere is found to increase with Ts at the rate of ~4 Wm-2 K-1 over tropical ocean regions of mean descending vertical motion. Precipitation (P) is tightly coupled to atmospheric radiative cooling rates and this implies an increase in P with warming at a slower rate than the observed increases in CWV. Since convective precipitation depends on moisture convergence, the above implies enhanced precipitation over convective regions and reduced precipitation over convectively suppressed regimes. To quantify this response, observed and simulated changes in precipitation rate are analysed separately over regions of mean ascending and descending vertical motion over the tropics. The observed response is found to be substantially larger than the model simulations and climate change projections. It is currently not clear whether this is due to deficiencies in model parametrizations or errors in satellite retrievals.

First CRDS-measurements of water vapour continuum in the 940nm absorption band

Measurements of near-infrared water vapour continuum using continuous wave cavity ring down spectroscopy (cw- CRDS) have been performed at around 10611.6 and 10685:2 cm1. The continuum absorption coefficients for N2- broadening have been determined for two temperatures and wavenumbers. These results represent the first near-IR continuum laboratory data determined within the complex spectral environment in the 940nm water vapour band and are in reasonable agreement with simulations using the semiempirical CKD formulation.

Evaluation of suitable spectral intervals for near-IR laboratory detection of water vapour continuum absorption

The water vapour continuum absorption is an important component of molecular absorption of radiation in atmosphere. However, uncertainty in knowledge of the value of the continuum absorption at present can achieve 100% in different spectral regions leading to an error in flux calculation up to 3-5 W/m2 global mean. This work uses line-by-line calculations to reveal the best spectral intervals for experimental verification of the CKD water vapour continuum models in the currently least studied near-infrared spectral region. Possible sources of errors in continuum retrieval taken into account in the simulation include the sensitivity of laboratory spectrometers and uncertainties in the spectral line parameters in HITRAN-2004 and Schwenke-Partridge database. It is shown that a number of micro-windows in near-IR can be used at present for laboratory detection of the water vapour continuum with estimated accuracy from 30 to 5%.

Intercomparison of radiative forcing calculations of stratospheric water vapour and contrails

Seven groups have participated in an intercomparison study of calculations of radiative forcing (RF) due to stratospheric water vapour (SWV) and contrails. A combination of detailed radiative transfer schemes and codes for global-scale calculations have been used, as well as a combination of idealized simulations and more realistic global-scale changes in stratospheric water vapour and contrails. Detailed line-by-line codes agree within about 15 % for longwave (LW) and shortwave (SW) RF, except in one case where the difference is 30 %. Since the LW and SW RF due to contrails and SWV changes are of opposite sign, the differences between the models seen in the individual LW and SW components can be either compensated or strengthened in the net RF, and thus in relative terms uncertainties are much larger for the net RF. Some of the models used for global-scale simulations of changes in SWV and contrails differ substantially in RF from the more detailed radiative transfer schemes. For the global-scale calculations we use a method of weighting the results to calculate a best estimate based on their performance compared to the more detailed radiative transfer schemes in the idealized simulations.

Accumulated metal speciation in earthworm populations with multi-generational exposure to metalliferous soils: cell fractionation and high energy synchrotron analyses

Predicting metal bioaccumulation and toxicity in soil organisms is complicated by site-specific biotic and abiotic parameters. In this study we exploited tissue fractionation and digestion techniques, combined with X-ray absorption spectroscopy (XAS), to investigate the whole-body and subcellular distributions, ligand affinities, and coordination chemistry of accumulated Pb and Zn in field populations of the epigeic earthworm Lumbricus rubellus inhabiting three contrasting metalliferous and two unpolluted soils. Our main findings were (i) earthworms were resident in soils with concentrations of Pb and Zn ranging from 1200 to 27 000 mg kg(-1) and 200 to 34 000 mg kg(-1), respectively; (ii) Pb and Zn primarily accumulated in the posterior alimentary canal in nonsoluble subcellular fractions of earthworms; (iii) site-specific differences in the tissue and subcellular partitioning profiles of populations were observed, with earthworms from a calcareous site partitioning proportionally more Pb to their anterior body segments and Zn to the chloragosome-rich subcellular fraction than their acidic-soil inhabiting counterparts; (iv) XAS indicated that the interpopulation differences in metal partitioning between organs were not accompanied by qualitative differences in ligand-binding speciation, because crystalline phosphate-containing pyromorphite was a predominant chemical species in the whole-worm tissues of all mine soil residents. Differences in metal (Pb, Zn) partitioning at both organ and cellular levels displayed by field populations with protracted histories of metal exposures may reflect their innate ecophysiological responses to essential edaphic variables, such as Ca2+ status. These observations are highly significant in the challenging exercise of interpreting holistic biomarker data delivered by "omic" technologies.

Evidence of heavy metal movement down the profile of a heavily-sludged soil

Two sites in central England where sewage sludge has been deposited for decades were studied to measure the heavy metal distribution in the soil profiles. The first site (S 1) was a field receiving heavy loads sludge from a nearby wastewater treatment plant, and the second (S2) was a farm applying 'normal' sludge rates of 8 t ha(-1) y(-1) of the same sludge. Soil samples were also taken by a near-by untreated control site. In S I the movement of heavy metals was significant even down to 80 cm depth compared to the control. In S2, the concentrations of lead (Pb) and zinc (Zn) and the organic matter content were higher than the control down to 20 cm, while nickel (Ni) moved significantly down to 80 cm. This underlies. the possibility that the metals bound onto organic surfaces moved along with organic matter down to that depth. The movement of metals in S2 points out the potential risks of applying sewage sludge for a long time.