Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

Two daily smoke maxima in eighteenth century London air

Varied electrostatics experiments followed Benjamin Franklin's pioneering atmospheric investigations. In Knightsbridge, Central London, John Read (1726–1814) installed a sensing rod in the upper part of his house and, using a pith ball electrometer and Franklin chimes, monitored atmospheric electricity from 1789 to 1791. Atmospheric electricity is sensitive to weather and smoke pollution. In calm weather conditions, Read observed two daily electrification maxima in moderate weather, around 9 am and 7 pm. This is likely to represent a double diurnal cycle in urban smoke. Before the motor car and steam railways, one source of the double maximum smoke pattern was the daily routine of fire lighting for domestic heating.

Estimating surface CO2 fluxes from space-borne dry air mole fraction observations using an Ensemble Kalman filter

We have developed an ensemble Kalman Filter (EnKF) to estimate 8-day regional surface fluxes of CO2 from space-borne CO2 dry-air mole fraction observations (XCO2) and evaluate the approach using a series of synthetic experiments, in preparation for data from the NASA Orbiting Carbon Observatory (OCO). The 32-day duty cycle of OCO alternates every 16 days between nadir and glint measurements of backscattered solar radiation at short-wave infrared wavelengths. The EnKF uses an ensemble of states to represent the error covariances to estimate 8-day CO2 surface fluxes over 144 geographical regions. We use a 12×8-day lag window, recognising that XCO2 measurements include surface flux information from prior time windows. The observation operator that relates surface CO2 fluxes to atmospheric distributions of XCO2 includes: a) the GEOS-Chem transport model that relates surface fluxes to global 3-D distributions of CO2 concentrations, which are sampled at the time and location of OCO measurements that are cloud-free and have aerosol optical depths <0.3; and b) scene-dependent averaging kernels that relate the CO2 profiles to XCO2, accounting for differences between nadir and glint measurements, and the associated scene-dependent observation errors. We show that OCO XCO2 measurements significantly reduce the uncertainties of surface CO2 flux estimates. Glint measurements are generally better at constraining ocean CO2 flux estimates. Nadir XCO2 measurements over the terrestrial tropics are sparse throughout the year because of either clouds or smoke. Glint measurements provide the most effective constraint for estimating tropical terrestrial CO2 fluxes by accurately sampling fresh continental outflow over neighbouring oceans. We also present results from sensitivity experiments that investigate how flux estimates change with 1) bias and unbiased errors, 2) alternative duty cycles, 3) measurement density and correlations, 4) the spatial resolution of estimated flux estimates, and 5) reducing the length of the lag window and the size of the ensemble. At the revision stage of this manuscript, the OCO instrument failed to reach its orbit after it was launched on 24 February 2009. The EnKF formulation presented here is also applicable to GOSAT measurements of CO2 and CH4.

Predicting mesh density for adaptive modelling of the global atmosphere

The shallow water equations are solved using a mesh of polygons on the sphere, which adapts infrequently to the predicted future solution. Infrequent mesh adaptation reduces the cost of adaptation and load-balancing and will thus allow for more accurate mapping on adaptation. We simulate the growth of a barotropically unstable jet adapting the mesh every 12 h. Using an adaptation criterion based largely on the gradient of the vorticity leads to a mesh with around 20 per cent of the cells of a uniform mesh that gives equivalent results. This is a similar proportion to previous studies of the same test case with mesh adaptation every 1–20 min. The prediction of the mesh density involves solving the shallow water equations on a coarse mesh in advance of the locally refined mesh in order to estimate where features requiring higher resolution will grow, decay or move to. The adaptation criterion consists of two parts: that resolved on the coarse mesh, and that which is not resolved and so is passively advected on the coarse mesh. This combination leads to a balance between resolving features controlled by the large-scale dynamics and maintaining fine-scale features.

Uncertainties in annual riverine phosphorus load estimation: Impact of load estimation methodology, sampling frequency, baseflow index and catchment population density

Models developed to identify the rates and origins of nutrient export from land to stream require an accurate assessment of the nutrient load present in the water body in order to calibrate model parameters and structure. These data are rarely available at a representative scale and in an appropriate chemical form except in research catchments. Observational errors associated with nutrient load estimates based on these data lead to a high degree of uncertainty in modelling and nutrient budgeting studies. Here, daily paired instantaneous P and flow data for 17 UK research catchments covering a total of 39 water years (WY) have been used to explore the nature and extent of the observational error associated with nutrient flux estimates based on partial fractions and infrequent sampling. The daily records were artificially decimated to create 7 stratified sampling records, 7 weekly records, and 30 monthly records from each WY and catchment. These were used to evaluate the impact of sampling frequency on load estimate uncertainty. The analysis underlines the high uncertainty of load estimates based on monthly data and individual P fractions rather than total P. Catchments with a high baseflow index and/or low population density were found to return a lower RMSE on load estimates when sampled infrequently than those with a tow baseflow index and high population density. Catchment size was not shown to be important, though a limitation of this study is that daily records may fail to capture the full range of P export behaviour in smaller catchments with flashy hydrographs, leading to an underestimate of uncertainty in Load estimates for such catchments. Further analysis of sub-daily records is needed to investigate this fully. Here, recommendations are given on load estimation methodologies for different catchment types sampled at different frequencies, and the ways in which this analysis can be used to identify observational error and uncertainty for model calibration and nutrient budgeting studies. (c) 2006 Elsevier B.V. All rights reserved.

Differentiating bone osteonal turnover rates by density fractionation; validation using the bomb C-14 atmospheric pulse

The density (BSG) of bone increases, at the osteon scale, during lifetime aging within the bone. In addition, post-mortem diagenetic change due to microbial attack produces denser bioapatite. Thus, fractionation of finely powdered bone on the basis of density should not only enable younger and older populations of osteons to be separated but also make it possible to separate out a less diagenetically altered component. We show that the density fractionation method can be used as a tool to investigate the isotopic history within an individual's lifetime, both in recent and archaeological contexts, and we use the bomb C-14 atmospheric pulse for validating the method.

Surface determination of the air-earth electrical current density using co-located sensors of different geometry

A vertical conduction current flows in the atmosphere as a result of the global atmospheric electric circuit. The current at the surface consists of the conduction current and a locally generated displacement current, which are often approximately equal in magnitude. A method of separating the two currents using two collectors of different geometry is investigated. The picoammeters connected to the collectors have a RC time constant of approximately 3 s, permitting the investigation of higher frequency air-earth current changes than previously achieved. The displacement current component of the air-earth current derived from the instrument agrees with calculations using simultaneous data from a co-located fast response electric field mill. The mean value of the nondisplacement current measured over 9 h was 1.76 +/- 0.002 pA m(-2). (c) 2006 American Institute of Physics.

Urban smoke concentrations at Kew, London, 1898-2004

Historical smoke concentrations at monthly resolution for the early twentieth century are found for Kew Observatory, London, using the atmospheric electricity proxy technique. Smoke particles modify the electrical properties of urban air: an increase in smoke concentration reduces air's electrical conductivity and increases the Potential Gradient (PG). Calibrated PG data are available from Kew since 1898, and air conductivity was measured routinely between 1909 and 1979 using the technique developed by C.T.R. Wilson. Automated smoke observations at the same site overlap with the atmospheric electrical measurements from 1921, providing an absolute calibration to smoke concentration. This shows that the late nineteenth century winter smoke concentrations at Kew were approximately 100 times greater than contemporary winter smoke concentrations. Following smoke emission regulations reducing the smoke concentration, the electrical parameters of the urban air did not change dramatically. This is suggested to be due to a composition change, with an increase in the abundance of small aerosol compensating for the decrease in smoke. (c) 2006 Elsevier Ltd. All rights reserved.

When smoke gets in our eyes: The multiple impacts of atmospheric black carbon on climate, air quality and health

With both climate change and air quality on political and social agendas from local to global scale, the links between these hitherto separate fields are becoming more apparent. Black carbon, largely from combustion processes, scatters and absorbs incoming solar radiation, contributes to poor air quality and induces respiratory and cardiovascular problems. Uncertainties in the amount, location, size and shape of atmospheric black carbon cause large uncertainty in both climate change estimates and toxicology studies alike. Increased research has led to new effects and areas of uncertainty being uncovered. Here we draw together recent results and explore the increasing opportunities for synergistic research that will lead to improved confidence in the impact of black carbon on climate change, air quality and human health. Topics of mutual interest include better information on spatial distribution, size, mixing state and measuring and monitoring. (c) 2006 Elsevier Ltd. All rights reserved.