pH effects on the complexation, miscibility and radiation-induced crosslinking in poly(acrylic acid)-poly (vinyl alcohol) blends

The effect of pH on the complexation of poly(acrylic acid) with poly(vinyl alcohol) in aqueous solution, the miscibility of these polymers in the solid state and the possibility for crosslinking the blends using gamma radiation has been studied. It is demonstrated that the complexation ability of poly(vinyl alcohol) with respect to poly(acrylic acid) is relatively low in comparison with some other synthetic non-ionic polymers. The precipitation of interpolymer complexes was observed below the critical pH of complexation (pH(crit1)), which characterizes the transition between a compact hydrophobic polycomplex and an extended hydrophilic interpolymer associate. Films prepared by casting from aqueous solutions at different pH values exhibited a transition from miscibility to immiscibility at a certain critical pH, pH(crit2), above which hydrogen bonding is prevented. It is shown here that gamma radiation crosslinking of solid blends is efficient and only results in the formation of hydrogel films for blends prepared between pH(crit1), and pH(crit2). The yield of the gel fraction and the swelling properties of the films depended on the absorbed radiation dose and the polymer ratio.

Simulation of the Earth's radiation budget by the European Centre for Medium-Range Weather Forecasts 40-year reanalysis (ERA40)

The radiation budget simulated by the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year reanalysis (ERA40) is evaluated for the period 1979–2001 using independent satellite data and additional model data. This provides information on the quality of the radiation products and indirect evaluation of other aspects of the climate produced by ERA40. The climatology of clear-sky outgoing longwave radiation (OLR) is well captured by ERA40. Underestimations of about 10 W m−2 in clear-sky OLR over tropical convective regions by ERA40 compared to satellite data are substantially reduced when the satellite sampling is taken into account. The climatology of column-integrated water vapor is well simulated by ERA40 compared to satellite data over the ocean, indicating that the simulation of downward clear-sky longwave fluxes at the surface is likely to be good. Clear-sky absorbed solar radiation (ASR) and clear-sky OLR are overestimated by ERA40 over north Africa and high-latitude land regions. The observed interannual changes in low-latitude means are not well reproduced. Using ERA40 to analyze trends and climate feedbacks globally is therefore not recommended. The all-sky radiation budget is poorly simulated by ERA40. OLR is overestimated by around 10 W m−2 over much of the globe. ASR is underestimated by around 30 W m−2 over tropical ocean regions. Away from marine stratocumulus regions, where cloud fraction is underestimated by ERA40, the poor radiation simulation by ERA40 appears to be related to inaccurate radiative properties of cloud rather than inaccurate cloud distributions.

Observed changes in top-of-the-atmosphere radiation and upper-ocean heating consistent within uncertainty

Global climate change results from a small yet persistent imbalance between the amount of sunlight absorbed by Earth and the thermal radiation emitted back to space. An apparent inconsistency has been diagnosed between interannual variations in the net radiation imbalance inferred from satellite measurements and upper-ocean heating rate from in situ measurements, and this inconsistency has been interpreted as ‘missing energy’ in the system. Here we present a revised analysis of net radiation at the top of the atmosphere from satellite data, and we estimate ocean heat content, based on three independent sources. We find that the difference between the heat balance at the top of the atmosphere and upper-ocean heat content change is not statistically significant when accounting for observational uncertainties in ocean measurements, given transitions in instrumentation and sampling. Furthermore, variability in Earth’s energy imbalance relating to El Niño-Southern Oscillation is found to be consistent within observational uncertainties among the satellite measurements, a reanalysis model simulation and one of the ocean heat content records. We combine satellite data with ocean measurements to depths of 1,800 m, and show that between January 2001 and December 2010, Earth has been steadily accumulating energy at a rate of 0.50±0.43 Wm−2 (uncertainties at the 90% confidence level). We conclude that energy storage is continuing to increase in the sub-surface ocean.

RAMI4PILPS: An intercomparison of formulations for the partitioning of solar radiation in land surface models

[1] Remotely sensed, multiannual data sets of shortwave radiative surface fluxes are now available for assimilation into land surface schemes (LSSs) of climate and/or numerical weather prediction models. The RAMI4PILPS suite of virtual experiments assesses the accuracy and consistency of the radiative transfer formulations that provide the magnitudes of absorbed, reflected, and transmitted shortwave radiative fluxes in LSSs. RAMI4PILPS evaluates models under perfectly controlled experimental conditions in order to eliminate uncertainties arising from an incomplete or erroneous knowledge of the structural, spectral and illumination related canopy characteristics typical for model comparison with in situ observations. More specifically, the shortwave radiation is separated into a visible and near-infrared spectral region, and the quality of the simulated radiative fluxes is evaluated by direct comparison with a 3-D Monte Carlo reference model identified during the third phase of the Radiation transfer Model Intercomparison (RAMI) exercise. The RAMI4PILPS setup thus allows to focus in particular on the numerical accuracy of shortwave radiative transfer formulations and to pinpoint to areas where future model improvements should concentrate. The impact of increasing degrees of structural and spectral subgrid variability on the simulated fluxes is documented and the relevance of any thus emerging biases with respect to gross primary production estimates and shortwave radiative forcings due to snow and fire events are investigated.

The response of the Southern Hemispheric eddy-driven jet to future changes in shortwave radiation in CMIP5

A strong relationship is found between changes in the meridional gradient of absorbed shortwave radiation (ASR) and Southern Hemispheric jet shifts in 21st century climate simulations of CMIP5 (Coupled Model Intercomparison Project phase 5) coupled models. The relationship is such that models with increases in the meridional ASR gradient around the southern midlatitudes, and therefore increases in midlatitude baroclinicity, tend to produce a larger poleward jet shift. The ASR changes are shown to be dominated by changes in cloud properties, with sea ice declines playing a secondary role. We demonstrate that the ASR changes are the cause, and not the result, of the intermodel differences in jet response by comparing coupled simulations with experiments in which sea surface temperature increases are prescribed. Our results highlight the importance of reducing the uncertainty in cloud feedbacks in order to constrain future circulation changes.

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

Observations of the diurnal cycle of outgoing longwave radiation from the Geostationary Earth Radiation Budget instrument

The Geostationary Earth Radiation Budget instrument on Meteosat-8, located over Africa, provides unprecedented temporal sampling (~17 minutes) of the broadband emitted thermal and reflected solar radiances. We analyse the diurnal cycle of the outgoing longwave radiation (OLR) fluxes derived from the thermal radiances for July 2006. Principal component (PC) analysis separates the signals of the surface temperature response to solar heating and of the development of convective clouds. The first two PCs explain most of the OLR variations: PC1 (surface heating) explains 82.3% of the total variance and PC2 (cloud development) explains 12.8% of the variance. Convection is initiated preferentially over mountainous regions and the cloud then advects downstream in the ambient flow. Diurnal variations are much weaker over the oceans, but a coherent signal over the Gulf of Guinea suggests that the cloudiness is modulated by the diurnally varying contrast between the Gulf and the adjacent land mass.

Evaluation of the Met Office global forecast model using Geostationary Earth Radiation Budget (GERB) data

Simulations of the top-of-atmosphere radiative-energy budget from the Met Office global numerical weather-prediction model are evaluated using new data from the Geostationary Earth Radiation Budget (GERB) instrument on board the Meteosat-8 satellite. Systematic discrepancies between the model simulations and GERB measurements greater than 20 Wm-2 in outgoing long-wave radiation (OLR) and greater than 60 Wm-2 in reflected short-wave radiation (RSR) are identified over the period April-September 2006 using 12 UTC data. Convective cloud over equatorial Africa is spatially less organized and less reflective than in the GERB data. This bias depends strongly on convective-cloud cover, which is highly sensitive to changes in the model convective parametrization. Underestimates in model OLR over the Gulf of Guinea coincide with unrealistic southerly cloud outflow from convective centres to the north. Large overestimates in model RSR over the subtropical ocean, greater than 50 Wm-2 at 12 UTC, are explained by unrealistic radiative properties of low-level cloud relating to overestimation of cloud liquid water compared with independent satellite measurements. The results of this analysis contribute to the development and improvement of parametrizations in the global forecast model.

Modeled and observed atmospheric radiation balance during the West African dry season: role of mineral dust, biomass burning aerosol, and surface albedo

The global radiation balance of the atmosphere is still poorly observed, particularly at the surface. We investigate the observed radiation balance at (1) the surface using the ARM Mobile Facility in Niamey, Niger, and (2) the top of the atmosphere (TOA) over West Africa using data from the Geostationary Earth Radiation Budget (GERB) instrument on board Meteosat-8. Observed radiative fluxes are compared with predictions from the global numerical weather prediction (NWP) version of the Met Office Unified Model (MetUM). The evaluation points to major shortcomings in the NWP model's radiative fluxes during the dry season (December 2005 to April 2006) arising from (1) a lack of absorbing aerosol in the model (mineral dust and biomass burning aerosol) and (2) a poor specification of the surface albedo. A case study of the major Saharan dust outbreak of 6–12 March 2006 is used to evaluate a parameterization of mineral dust for use in the NWP models. The model shows good predictability of the large-scale flow out to 4–5 days with the dust parameterization providing reasonable dust uplift, spatial distribution, and temporal evolution for this strongly forced dust event. The direct radiative impact of the dust reduces net downward shortwave (SW) flux at the surface (TOA) by a maximum of 200 W m−2 (150 W m−2), with a SW heating of the atmospheric column. The impacts of dust on terrestrial radiation are smaller. Comparisons of TOA (surface) radiation balance with GERB (ARM) show the “dusty” forecasts reduce biases in the radiative fluxes and improve surface temperatures and vertical thermodynamic structure.

Tripleclouds: an efficient method for representing horizontal cloud inhomogeneity in 1D radiation schemes by using three regions at each height

Radiation schemes in general circulation models currently make a number of simplifications when accounting for clouds, one of the most important being the removal of horizontal inhomogeneity. A new scheme is presented that attempts to account for the neglected inhomogeneity by using two regions of cloud in each vertical level of the model as opposed to one. One of these regions is used to represent the optically thinner cloud in the level, and the other represents the optically thicker cloud. So, along with the clear-sky region, the scheme has three regions in each model level and is referred to as “Tripleclouds.” In addition, the scheme has the capability to represent arbitrary vertical overlap between the three regions in pairs of adjacent levels. This scheme is implemented in the Edwards–Slingo radiation code and tested on 250 h of data from 12 different days. The data are derived from cloud retrievals using radar, lidar, and a microwave radiometer at Chilbolton, southern United Kingdom. When the data are grouped into periods equivalent in size to general circulation model grid boxes, the shortwave plane-parallel albedo bias is found to be 8%, while the corresponding bias is found to be less than 1% using Tripleclouds. Similar results are found for the longwave biases. Tripleclouds is then compared to a more conventional method of accounting for inhomogeneity that multiplies optical depths by a constant scaling factor, and Tripleclouds is seen to improve on this method both in terms of top-of-atmosphere radiative flux biases and internal heating rates.

Sampling uncertainties in surface radiation budget calculations in RADAGAST

In the Radiative Atmospheric Divergence Using ARM Mobile Facility GERB and AMMA Stations (RADAGAST) project we calculate the divergence of radiative flux across the atmosphere by comparing fluxes measured at each end of an atmospheric column above Niamey, in the African Sahel region. The combination of broadband flux measurements from geostationary orbit and the deployment for over 12 months of a comprehensive suite of active and passive instrumentation at the surface eliminates a number of sampling issues that could otherwise affect divergence calculations of this sort. However, one sampling issue that challenges the project is the fact that the surface flux data are essentially measurements made at a point, while the top-of-atmosphere values are taken over a solid angle that corresponds to an area at the surface of some 2500 km2. Variability of cloud cover and aerosol loading in the atmosphere mean that the downwelling fluxes, even when averaged over a day, will not be an exact match to the area-averaged value over that larger area, although we might expect that it is an unbiased estimate thereof. The heterogeneity of the surface, for example, fixed variations in albedo, further means that there is a likely systematic difference in the corresponding upwelling fluxes. In this paper we characterize and quantify this spatial sampling problem. We bound the root-mean-square error in the downwelling fluxes by exploiting a second set of surface flux measurements from a site that was run in parallel with the main deployment. The differences in the two sets of fluxes lead us to an upper bound to the sampling uncertainty, and their correlation leads to another which is probably optimistic as it requires certain other conditions to be met. For the upwelling fluxes we use data products from a number of satellite instruments to characterize the relevant heterogeneities and so estimate the systematic effects that arise from the flux measurements having to be taken at a single point. The sampling uncertainties vary with the season, being higher during the monsoon period. We find that the sampling errors for the daily average flux are small for the shortwave irradiance, generally less than 5 W m−2, under relatively clear skies, but these increase to about 10 W m−2 during the monsoon. For the upwelling fluxes, again taking daily averages, systematic errors are of order 10 W m−2 as a result of albedo variability. The uncertainty on the longwave component of the surface radiation budget is smaller than that on the shortwave component, in all conditions, but a bias of 4 W m−2 is calculated to exist in the surface leaving longwave flux.

Examination of Relationships between Clear-Sky Longwave Radiation and Aspects of the Atmospheric Hydrological Cycle in Climate Models, Reanalyses, and Observations

Relationships between clear-sky longwave radiation and aspects of the atmospheric hydrological cycle are quantified in models, reanalyses, and observations over the period 1980-2000. The robust sensitivity of clear-sky surface net longwave radiation (SNLc) to column-integrated water vapor (CWV) of 1-1.5 Wm(-2) mm(-1) combined with the positive relationship between CWV and surface temperature (T-s) explains substantial increases in clear-sky longwave radiative cooling of the atmosphere (Q(LWc)) to the surface over the period. Clear-sky outgoing longwave radiation (OLRc) is highly sensitive to changes in aerosol and greenhouse gas concentrations in addition to temperature and humidity. Over tropical ocean regions of mean descent, Q(LWc) increases with T-s at similar to 3.5-5.5 W m(-2) K-1 for reanalyses, estimates derived from satellite data, and models without volcanic forcing included. Increased Q(LWc) with warming across the tropical oceans helps to explain model ensemble mean increases in precipitation of 0.1-0.15 mm day(-1) K-1, which are primarily determined by ascent regions where precipitation increases at the rate expected from the Clausius-Clapeyron equation. The implications for future projections in the atmospheric hydrological cycle are discussed

Can desert dust explain the outgoing longwave radiation anomaly over the Sahara during July 2003?

Measurements of the top‐of‐the‐atmosphere outgoing longwave radiation (OLR) for July 2003 from Meteosat‐7 are used to assess the performance of the numerical weather prediction version of the Met Office Unified Model. A significant difference is found over desert regions of northern Africa where the model emits too much OLR by up to 35 Wm−2 in the monthly mean. By cloud‐screening the data we find an error of up to 50 Wm−2 associated with cloud‐free areas, which suggests an error in the model surface temperature, surface emissivity, or atmospheric transmission. By building up a physical model of the radiative properties of mineral dust based on in situ, and surface‐based and satellite remote sensing observations we show that the most plausible explanation for the discrepancy in OLR is due to the neglect of mineral dust in the model. The calculations suggest that mineral dust can exert a longwave radiative forcing by as much as 50 Wm−2 in the monthly mean for 1200 UTC in cloud‐free regions, which accounts for the discrepancy between the model and the Meteosat‐7 observations. This suggests that inclusion of the radiative effects of mineral dust will lead to a significant improvement in the radiation balance of numerical weather prediction models with subsequent improvements in performance.