Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

Perfluorodecalin: global warming potential and first detection in the atmosphere

Perfluorodecalin (C10F18) has a range of medical uses that have led to small releases. Recently, it has been proposed as a carrier of vaccines, which could lead to significantly larger emissions. Since its emissions are controlled under the Kyoto Protocol, it is important that values for the global warming potential (GWP) are available. For a 50:50 mixture of the two isomers of perfluorodecalin, laboratory measurements, supplemented by theoretical calculations, give an integrated absorption cross-section of 3.91 x 10(-16) cm(2) molecule(-1) cm(-1) over the spectral region 0-1500 cm(-1); calculations yield a radiative efficiency of 0.56 W m(-2) ppbv(-1) and a 100-year GWP, relative to carbon dioxide, of 7200 assuming a lifetime of 1000 years. We report the first atmospheric measurements of perfluorodecalin, at Bristol, UK and Mace Head, Ireland, where volume mixing ratios are about 1.5 x 10(-15). At these concentrations, it makes a trivial contribution to climate change, but on a per molecule basis it is a potent greenhouse gas, indicating the need for careful assessment of its possible future usage. (c) 2005 Elsevier Ltd. All rights reserved.

Multiple-scattering in radar systems: a review

Although extensively studied within the lidar community, the multiple scattering phenomenon has always been considered a rare curiosity by radar meteorologists. Up to few years ago its appearance has only been associated with two- or three-body-scattering features (e.g. hail flares and mirror images) involving highly reflective surfaces. Recent atmospheric research aimed at better understanding of the water cycle and the role played by clouds and precipitation in affecting the Earth's climate has driven the deployment of high frequency radars in space. Examples are the TRMM 13.5 GHz, the CloudSat 94 GHz, the upcoming EarthCARE 94 GHz, and the GPM dual 13-35 GHz radars. These systems are able to detect the vertical distribution of hydrometeors and thus provide crucial feedbacks for radiation and climate studies. The shift towards higher frequencies increases the sensitivity to hydrometeors, improves the spatial resolution and reduces the size and weight of the radar systems. On the other hand, higher frequency radars are affected by stronger extinction, especially in the presence of large precipitating particles (e.g. raindrops or hail particles), which may eventually drive the signal below the minimum detection threshold. In such circumstances the interpretation of the radar equation via the single scattering approximation may be problematic. Errors will be large when the radiation emitted from the radar after interacting more than once with the medium still contributes substantially to the received power. This is the case if the transport mean-free-path becomes comparable with the instrument footprint (determined by the antenna beam-width and the platform altitude). This situation resembles to what has already been experienced in lidar observations, but with a predominance of wide- versus small-angle scattering events. At millimeter wavelengths, hydrometeors diffuse radiation rather isotropically compared to the visible or near infrared region where scattering is predominantly in the forward direction. A complete understanding of radiation transport modeling and data analysis methods under wide-angle multiple scattering conditions is mandatory for a correct interpretation of echoes observed by space-borne millimeter radars. This paper reviews the status of research in this field. Different numerical techniques currently implemented to account for higher order scattering are reviewed and their weaknesses and strengths highlighted. Examples of simulated radar backscattering profiles are provided with particular emphasis given to situations in which the multiple scattering contributions become comparable or overwhelm the single scattering signal. We show evidences of multiple scattering effects from air-borne and from CloudSat observations, i.e. unique signatures which cannot be explained by single scattering theory. Ideas how to identify and tackle the multiple scattering effects are discussed. Finally perspectives and suggestions for future work are outlined. This work represents a reference-guide for studies focused at modeling the radiation transport and at interpreting data from high frequency space-borne radar systems that probe highly opaque scattering media such as thick ice clouds or precipitating clouds.

Effect of improving representation of horizontal and vertical cloud structure on the Earth's global radiation budget. Part I: review and parametrization

A poor representation of cloud structure in a general circulation model (GCM) is widely recognised as a potential source of error in the radiation budget. Here, we develop a new way of representing both horizontal and vertical cloud structure in a radiation scheme. This combines the ‘Tripleclouds’ parametrization, which introduces inhomogeneity by using two cloudy regions in each layer as opposed to one, each with different water content values, with ‘exponential-random’ overlap, in which clouds in adjacent layers are not overlapped maximally, but according to a vertical decorrelation scale. This paper, Part I of two, aims to parametrize the two effects such that they can be used in a GCM. To achieve this, we first review a number of studies for a globally applicable value of fractional standard deviation of water content for use in Tripleclouds. We obtain a value of 0.75 ± 0.18 from a variety of different types of observations, with no apparent dependence on cloud type or gridbox size. Then, through a second short review, we create a parametrization of decorrelation scale for use in exponential-random overlap, which varies the scale linearly with latitude from 2.9 km at the Equator to 0.4 km at the poles. When applied to radar data, both components are found to have radiative impacts capable of offsetting biases caused by cloud misrepresentation. Part II of this paper implements Tripleclouds and exponential-random overlap into a radiation code and examines both their individual and combined impacts on the global radiation budget using re-analysis data.

Effect of improving representation of horizontal and vertical cloud structure on the Earth's global radiation budget. Part II: The global effects

Reliably representing both horizontal cloud inhomogeneity and vertical cloud overlap is fundamentally important for the radiation budget of a general circulation model. Here, we build on the work of Part One of this two-part paper by applying a pair of parameterisations that account for horizontal inhomogeneity and vertical overlap to global re-analysis data. These are applied both together and separately in an attempt to quantify the effects of poor representation of the two components on radiation budget. Horizontal inhomogeneity is accounted for using the “Tripleclouds” scheme, which uses two regions of cloud in each layer of a gridbox as opposed to one; vertical overlap is accounted for using “exponential-random” overlap, which aligns vertically continuous cloud according to a decorrelation height. These are applied to a sample of scenes from a year of ERA-40 data. The largest radiative effect of horizontal inhomogeneity is found to be in areas of marine stratocumulus; the effect of vertical overlap is found to be fairly uniform, but with larger individual short-wave and long-wave effects in areas of deep, tropical convection. The combined effect of the two parameterisations is found to reduce the magnitude of the net top-of-atmosphere cloud radiative forcing (CRF) by 2.25 W m−2, with shifts of up to 10 W m−2 in areas of marine stratocumulus. The effects of the uncertainty in our parameterisations on radiation budget is also investigated. It is found that the uncertainty in the impact of horizontal inhomogeneity is of order ±60%, while the uncertainty in the impact of vertical overlap is much smaller. This suggests an insensitivity of the radiation budget to the exact nature of the global decorrelation height distribution derived in Part One.

The global atmospheric electrical circuit and climate

Evidence is emerging for physical links among clouds, global temperatures, the global atmospheric electrical circuit and cosmic ray ionisation. The global circuit extends throughout the atmosphere from the planetary surface to the lower layers of the ionosphere. Cosmic rays are the principal source of atmospheric ions away from the continental boundary layer: the ions formed permit a vertical conduction current to flow in the fair weather part of the global circuit. Through the (inverse) solar modulation of cosmic rays, the resulting columnar ionisation changes may allow the global circuit to convey a solar influence to meteorological phenomena of the lower atmosphere. Electrical effects on non-thunderstorm clouds have been proposed to occur via the ion-assisted formation of ultra-fine aerosol, which can grow to sizes able to act as cloud condensation nuclei, or through the increased ice nucleation capability of charged aerosols. Even small atmospheric electrical modulations on the aerosol size distribution can affect cloud properties and modify the radiative balance of the atmosphere, through changes communicated globally by the atmospheric electrical circuit. Despite a long history of work in related areas of geophysics, the direct and inverse relationships between the global circuit and global climate remain largely quantitatively unexplored. From reviewing atmospheric electrical measurements made over two centuries and possible paleoclimate proxies, global atmospheric electrical circuit variability should be expected on many timescales

Vertical velocity variance and skewness in clear and cloud-topped boundary layers as revealed by Doppler lidar

In this paper, observations by a ground-based vertically pointing Doppler lidar and sonic anemometer are used to investigate the diurnal evolution of boundary-layer turbulence in cloudless, cumulus and stratocumulus conditions. When turbulence is driven primarily by surface heating, such as in cloudless and cumulus-topped boundary layers, both the vertical velocity variance and skewness follow similar profiles, on average, to previous observational studies of turbulence in convective conditions, with a peak skewness of around 0.8 in the upper third of the mixed layer. When the turbulence is driven primarily by cloud-top radiative cooling, such as in the presence of nocturnal stratocumulus, it is found that the skewness is inverted in both sign and height: its minimum value of around −0.9 occurs in the lower third of the mixed layer. The profile of variance is consistent with a cloud-top cooling rate of around 30Wm−2. This is also consistent with the evolution of the thermodynamic profile and the rate of growth of the mixed layer into the stable nocturnal boundary layer from above. In conditions where surface heating occurs simultaneously with cloud-top cooling, the skewness is found to be useful for diagnosing the source of the turbulence, suggesting that long-term Doppler lidar observations would be valuable for evaluating boundary-layer parametrization schemes. Copyright c 2009 Royal Meteorological Society

U.K. HiGEM: Simulations of desert dust and biomass burning aerosols with a high-resolution atmospheric GCM

The atmospheric component of the United Kingdom’s new High-resolution Global Environmental Model (HiGEM) has been run with interactive aerosol schemes that include biomass burning and mineral dust. Dust emission, transport, and deposition are parameterized within the model using six particle size divisions, which are treated independently. The biomass is modeled in three nonindependent modes, and emissions are prescribed from an external dataset. The model is shown to produce realistic horizontal and vertical distributions of these aerosols for each season when compared with available satellite- and ground-based observations and with other models. Combined aerosol optical depths off the coast of North Africa exceed 0.5 both in boreal winter, when biomass is the main contributor, and also in summer, when the dust dominates. The model is capable of resolving smaller-scale features, such as dust storms emanating from the Bode´ le´ and Saharan regions of North Africa and the wintertime Bode´ le´ low-level jet. This is illustrated by February and July case studies, in which the diurnal cycles of model variables in relation to dust emission and transport are examined. The top-of-atmosphere annual mean radiative forcing of the dust is calculated and found to be globally quite small but locally very large, exceeding 20 W m22 over the Sahara, where inclusion of dust aerosol is shown to improve the model radiative balance. This work extends previous aerosol studies by combining complexity with increased global resolution and represents a step toward the next generation of models to investigate aerosol–climate interactions. 1. Introduction Accurate modeling of mineral dust is known to be important because of its radiative impact in both numerical weather prediction models (Milton et al. 2008; Haywood et

An assessment of aerosol‐cloud interactions in marine stratus clouds based on surface remote sensing

An assessment of aerosol-cloud interactions (ACI) from ground-based remote sensing under coastal stratiform clouds is presented. The assessment utilizes a long-term, high temporal resolution data set from the Atmospheric Radiation Measurement (ARM) Program deployment at Pt. Reyes, California, United States, in 2005 to provide statistically robust measures of ACI and to characterize the variability of the measures based on variability in environmental conditions and observational approaches. The average ACIN (= dlnNd/dlna, the change in cloud drop number concentration with aerosol concentration) is 0.48, within a physically plausible range of 0–1.0. Values vary between 0.18 and 0.69 with dependence on (1) the assumption of constant cloud liquid water path (LWP), (2) the relative value of cloud LWP, (3) methods for retrieving Nd, (4) aerosol size distribution, (5) updraft velocity, and (6) the scale and resolution of observations. The sensitivity of the local, diurnally averaged radiative forcing to this variability in ACIN values, assuming an aerosol perturbation of 500 c-3 relative to a background concentration of 100 cm-3, ranges betwee-4 and -9 W -2. Further characterization of ACI and its variability is required to reduce uncertainties in global radiative forcing estimates.

Remote sensing of cloud properties using ground-based measurements of zenith radiance

We have conducted the first extensive field test of two new methods to retrieve optical properties for overhead clouds that range from patchy to overcast. The methods use measurements of zenith radiance at 673 and 870 nm wavelengths and require the presence of green vegetation in the surrounding area. The test was conducted at the Atmospheric Radiation Measurement Program Oklahoma site during September–November 2004. These methods work because at 673 nm (red) and 870 nm (near infrared (NIR)), clouds have nearly identical optical properties, while vegetated surfaces reflect quite differently. The first method, dubbed REDvsNIR, retrieves not only cloud optical depth τ but also radiative cloud fraction. Because of the 1-s time resolution of our radiance measurements, we are able for the first time to capture changes in cloud optical properties at the natural timescale of cloud evolution. We compared values of τ retrieved by REDvsNIR to those retrieved from downward shortwave fluxes and from microwave brightness temperatures. The flux method generally underestimates τ relative to the REDvsNIR method. Even for overcast but inhomogeneous clouds, differences between REDvsNIR and the flux method can be as large as 50%. In addition, REDvsNIR agreed to better than 15% with the microwave method for both overcast and broken clouds. The second method, dubbed COUPLED, retrieves τ by combining zenith radiances with fluxes. While extra information from fluxes was expected to improve retrievals, this is not always the case. In general, however, the COUPLED and REDvsNIR methods retrieve τ to within 15% of each other.

Precipitation and latent heating distributions from satellite passive microwave radiometry. Part I: improved method and uncertainties

A revised Bayesian algorithm for estimating surface rain rate, convective rain proportion, and latent heating profiles from satellite-borne passive microwave radiometer observations over ocean backgrounds is described. The algorithm searches a large database of cloud-radiative model simulations to find cloud profiles that are radiatively consistent with a given set of microwave radiance measurements. The properties of these radiatively consistent profiles are then composited to obtain best estimates of the observed properties. The revised algorithm is supported by an expanded and more physically consistent database of cloud-radiative model simulations. The algorithm also features a better quantification of the convective and nonconvective contributions to total rainfall, a new geographic database, and an improved representation of background radiances in rain-free regions. Bias and random error estimates are derived from applications of the algorithm to synthetic radiance data, based upon a subset of cloud-resolving model simulations, and from the Bayesian formulation itself. Synthetic rain-rate and latent heating estimates exhibit a trend of high (low) bias for low (high) retrieved values. The Bayesian estimates of random error are propagated to represent errors at coarser time and space resolutions, based upon applications of the algorithm to TRMM Microwave Imager (TMI) data. Errors in TMI instantaneous rain-rate estimates at 0.5°-resolution range from approximately 50% at 1 mm h−1 to 20% at 14 mm h−1. Errors in collocated spaceborne radar rain-rate estimates are roughly 50%–80% of the TMI errors at this resolution. The estimated algorithm random error in TMI rain rates at monthly, 2.5° resolution is relatively small (less than 6% at 5 mm day−1) in comparison with the random error resulting from infrequent satellite temporal sampling (8%–35% at the same rain rate). Percentage errors resulting from sampling decrease with increasing rain rate, and sampling errors in latent heating rates follow the same trend. Averaging over 3 months reduces sampling errors in rain rates to 6%–15% at 5 mm day−1, with proportionate reductions in latent heating sampling errors.

The effect of surface heterogeneity on cloud absorption estimates

This study presents a systematic and quantitative analysis of the effect of inhomogeneous surface albedo on shortwave cloud absorption estimates. We used 3D radiative transfer modeling over a checkerboard surface albedo to calculate cloud absorption. We have found that accounting for surface heterogeneity enhances cloud absorption. However, the enhancement is not sufficient to explain the reported difference between measured and modeled cloud absorption.

The impact of traffic emissions on atmospheric ozone and OH: results from QUANTIFY

To estimate the impact of emissions by road, aircraft and ship traffic on ozone and OH in the present-day atmosphere six different atmospheric chemistry models have been used. Based on newly developed global emission inventories for road, ship and aircraft emission data sets each model performed sensitivity simulations reducing the emissions of each transport sector by 5%. The model results indicate that on global annual average lower tropospheric ozone responds most sensitive to ship emissions (50.6%±10.9% of the total traffic induced perturbation), followed by road (36.7%±9.3%) and aircraft exhausts (12.7%±2.9%), respectively. In the northern upper troposphere between 200–300 hPa at 30–60° N the maximum impact from road and ship are 93% and 73% of the maximum effect of aircraft, respectively. The latter is 0.185 ppbv for ozone (for the 5% case) or 3.69 ppbv when scaling to 100%. On the global average the impact of road even dominates in the UTLS-region. The sensitivity of ozone formation per NOx molecule emitted is highest for aircraft exhausts. The local maximum effect of the summed traffic emissions on the ozone column predicted by the models is 0.2 DU and occurs over the northern subtropical Atlantic extending to central Europe. Below 800 hPa both ozone and OH respond most sensitively to ship emissions in the marine lower troposphere over the Atlantic. Based on the 5% perturbation the effect on ozone can exceed 0.6% close to the marine surface (global zonal mean) which is 80% of the total traffic induced ozone perturbation. In the southern hemisphere ship emissions contribute relatively strongly to the total ozone perturbation by 60%–80% throughout the year. Methane lifetime changes against OH are affected strongest by ship emissions up to 0.21 (± 0.05)%, followed by road (0.08 (±0.01)%) and air traffic (0.05 (± 0.02)%). Based on the full scale ozone and methane perturbations positive radiative forcings were calculated for road emissions (7.3±6.2 mWm−2) and for aviation (2.9±2.3 mWm−2). Ship induced methane lifetime changes dominate over the ozone forcing and therefore lead to a net negative forcing (−25.5±13.2 mWm−2).

Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn

The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.

Transport impacts on atmosphere and climate: metrics

The transport sector emits a wide variety of gases and aerosols, with distinctly different characteristics which influence climate directly and indirectly via chemical and physical processes. Tools that allow these emissions to be placed on some kind of common scale in terms of their impact on climate have a number of possible uses such as: in agreements and emission trading schemes; when considering potential trade-offs between changes in emissions resulting from technological or operational developments; and/or for comparing the impact of different environmental impacts of transport activities. Many of the non-CO2 emissions from the transport sector are short-lived substances, not currently covered by the Kyoto Protocol. There are formidable difficulties in developing metrics and these are particularly acute for such short-lived species. One difficulty concerns the choice of an appropriate structure for the metric (which may depend on, for example, the design of any climate policy it is intended to serve) and the associated value judgements on the appropriate time periods to consider; these choices affect the perception of the relative importance of short- and long-lived species. A second difficulty is the quantification of input parameters (due to underlying uncertainty in atmospheric processes). In addition, for some transport-related emissions, the values of metrics (unlike the gases included in the Kyoto Protocol) depend on where and when the emissions are introduced into the atmosphere – both the regional distribution and, for aircraft, the distribution as a function of altitude, are important. In this assessment of such metrics, we present Global Warming Potentials (GWPs) as these have traditionally been used in the implementation of climate policy. We also present Global Temperature Change Potentials (GTPs) as an alternative metric, as this, or a similar metric may be more appropriate for use in some circumstances. We use radiative forcings and lifetimes from the literature to derive GWPs and GTPs for the main transport-related emissions, and discuss the uncertainties in these estimates. We find large variations in metric (GWP and GTP) values for NOx, mainly due to the dependence on location of emissions but also because of inter-model differences and differences in experimental design. For aerosols we give only global-mean values due to an inconsistent picture amongst available studies regarding regional dependence. The uncertainty in the presented metric values reflects the current state of understanding; the ranking of the various components with respect to our confidence in the given metric values is also given. While the focus is mostly on metrics for comparing the climate impact of emissions, many of the issues are equally relevant for stratospheric ozone depletion metrics, which are also discussed.