Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

On the use of geometric moments to examine the continuum of sudden stratospheric warmings

The polar winter stratospheric vortex is a coherent structure that undergoes different types of deformation that can be revealed by the geometric invariant moments. Three moments are used—the aspect ratio, the centroid latitude, and the area of the vortex based on stratospheric data from the 40-yr ECMWF Re-Analysis (ERA-40) project—to study sudden stratospheric warmings. Hierarchical clustering combined with data image visualization techniques is used as well. Using the gap statistic, three optimal clusters are obtained based on the three geometric moments considered here. The 850-K potential vorticity field, as well as the vertical profiles of polar temperature and zonal wind, provides evidence that the clusters represent, respectively, the undisturbed (U), displaced (D), and split (S) states of the polar vortex. This systematic method for identifying and characterizing the state of the polar vortex using objective methods is useful as a tool for analyzing observations and as a test for climate models to simulate the observations. The method correctly identifies all previously identified major warmings and also identifies significant minor warmings where the atmosphere is substantially disturbed but does not quite meet the criteria to qualify as a major stratospheric warming.

Influence of dynamics on the changes in tropical cloud radiative forcing during the 1998 El Niño

Satellite measurements of the radiation budget and data from the U.S. National Centers for Environmental Prediction–National Center for Atmospheric Research reanalysis are used to investigate the links between anomalous cloud radiative forcing over the tropical west Pacific warm pool and the tropical dynamics and sea surface temperature (SST) distribution during 1998. The ratio, N, of the shortwave cloud forcing (SWCF) to longwave cloud forcing (LWCF) (N = −SWCF/LWCF) is used to infer information on cloud altitude. A higher than average N during 1998 appears to be related to two separate phenomena. First, dynamic regime-dependent changes explain high values of N (associated with low cloud altitude) for small magnitudes of SWCF and LWCF (low cloud fraction), which reflect the unusual occurrence of mean subsiding motion over the tropical west Pacific during 1998, associated with the anomalous SST distribution. Second, Tropics-wide long-term changes in the spatial-mean cloud forcing, independent of dynamic regime, explain the higher values of N during both 1998 and in 1994/95. The changes in dynamic regime and their anomalous structure in 1998 are well simulated by version HadAM3 of the Hadley Centre climate model, forced by the observed SSTs. However, the LWCF and SWCF are poorly simulated, as are the interannual changes in N. It is argued that improved representation of LWCF and SWCF and their dependence on dynamical forcing are required before the cloud feedbacks simulated by climate models can be trusted.

Evaluating the potential for statistical decadal predictions of sea surface temperatures with a perfect model approach

We explore the potential for making statistical decadal predictions of sea surface temperatures (SSTs) in a perfect model analysis, with a focus on the Atlantic basin. Various statistical methods (Lagged correlations, Linear Inverse Modelling and Constructed Analogue) are found to have significant skill in predicting the internal variability of Atlantic SSTs for up to a decade ahead in control integrations of two different global climate models (GCMs), namely HadCM3 and HadGEM1. Statistical methods which consider non-local information tend to perform best, but which is the most successful statistical method depends on the region considered, GCM data used and prediction lead time. However, the Constructed Analogue method tends to have the highest skill at longer lead times. Importantly, the regions of greatest prediction skill can be very different to regions identified as potentially predictable from variance explained arguments. This finding suggests that significant local decadal variability is not necessarily a prerequisite for skillful decadal predictions, and that the statistical methods are capturing some of the dynamics of low-frequency SST evolution. In particular, using data from HadGEM1, significant skill at lead times of 6–10 years is found in the tropical North Atlantic, a region with relatively little decadal variability compared to interannual variability. This skill appears to come from reconstructing the SSTs in the far north Atlantic, suggesting that the more northern latitudes are optimal for SST observations to improve predictions. We additionally explore whether adding sub-surface temperature data improves these decadal statistical predictions, and find that, again, it depends on the region, prediction lead time and GCM data used. Overall, we argue that the estimated prediction skill motivates the further development of statistical decadal predictions of SSTs as a benchmark for current and future GCM-based decadal climate predictions.

Dependence of Indian monsoon rainfall on moisture fluxes across the Arabian Sea and the impact of coupled model sea surface temperature biases

The Arabian Sea is an important moisture source for Indian monsoon rainfall. The skill of climate models in simulating the monsoon and its variability varies widely, while Arabian Sea cold sea surface temperature (SST) biases are common in coupled models and may therefore influence the monsoon and its sensitivity to climate change. We examine the relationship between monsoon rainfall, moisture fluxes and Arabian Sea SST in observations and climate model simulations. Observational analysis shows strong monsoons depend on moisture fluxes across the Arabian Sea, however detecting consistent signals with contemporaneous summer SST anomalies is complicated in the observed system by air/sea coupling and large-scale induced variability such as the El Niño-Southern Oscillation feeding back onto the monsoon through development of the Somali Jet. Comparison of HadGEM3 coupled and atmosphere-only configurations suggests coupled model cold SST biases significantly reduce monsoon rainfall. Idealised atmosphere-only experiments show that the weakened monsoon can be mainly attributed to systematic Arabian Sea cold SST biases during summer and their impact on the monsoon-moisture relationship. The impact of large cold SST biases on atmospheric moisture content over the Arabian Sea, and also the subsequent reduced latent heat release over India, dominates over any enhancement in the land-sea temperature gradient and results in changes to the mean state. We hypothesize that a cold base state will result in underestimation of the impact of larger projected Arabian Sea SST changes in future climate, suggesting that Arabian Sea biases should be a clear target for model development.

High frequency variability of the Atlantic meridional overturning circulation

We compare the variability of the Atlantic meridional overturning circulation (AMOC) as simulated by the coupled climate models of the RAPID project, which cover a wide range of resolution and complexity, and observed by the RAPID/MOCHA array at about 26N. We analyse variability on a range of timescales, from five-daily to interannual. In models of all resolutions there is substantial variability on timescales of a few days; in most AOGCMs the amplitude of the variability is of somewhat larger magnitude than that observed by the RAPID array, while the time-mean is within about 10% of the observational estimate. The amplitude of the simulated annual cycle is similar to observations, but the shape of the annual cycle shows a spread among the models. A dynamical decomposition shows that in the models, as in observations, the AMOC is predominantly geostrophic (driven by pressure and sea-level gradients), with both geostrophic and Ekman contributions to variability, the latter being exaggerated and the former underrepresented in models. Other ageostrophic terms, neglected in the observational estimate, are small but not negligible. The time-mean of the western boundary current near the latitude of the RAPID/MOCHA array has a much wider model spread than the AMOC does, indicating large differences among models in the simulation of the wind-driven gyre circulation, and its variability is unrealistically small in the models. In many RAPID models and in models of the Coupled Model Intercomparison Project Phase 3 (CMIP3), interannual variability of the maximum of the AMOC wherever it lies, which is a commonly used model index, is similar to interannual variability in the AMOC at 26N. Annual volume and heat transport timeseries at the same latitude are well-correlated within 15--45N, indicating the climatic importance of the AMOC. In the RAPID and CMIP3 models, we show that the AMOC is correlated over considerable distances in latitude, but not the whole extent of the north Atlantic; consequently interannual variability of the AMOC at 50N, where it is particularly relevant to European climate, is not well-correlated with that of the AMOC at 26N, where it is monitored by the RAPID/MOCHA array.

Spin-up and adjustment of the Antarctic Circumpolar Current and global pycnocline

A theory is presented for the adjustment of the Antarctic Circumpolar Current (ACC) and global pycnocline to a sudden and sustained change in wind forcing. The adjustment timescale is controlled by the mesoscale eddy diffusivity across the ACC, the mean width of the ACC, the surface area of the ocean basins to the north, and deep water formation in the North Atlantic. In particular, northern sinking may have the potential to shorten the timescale and reduce its sensitivity to Southern Ocean eddies, but the relative importance of northern sinking and Southern Ocean eddies cannot be determined precisely, largely due to limitations in the parameterization of northern sinking. Although it is clear that the main processes that control the adjustment timescale are those which counteract the deepening of the global pycnocline, the theory also suggests that the timescale can be subtly modified by wind forcing over the ACC and global diapycnal mixing. Results from calculations with a reduced-gravity model compare well with the theory. The multidecadal-centennial adjustment timescale implies that long observational time series will be required to detect dynamic change in the ACC due to anthropogenic forcing. The potential role of Southern Ocean mesoscale eddy activity in determining both the equilibrium state of the ACC and the timescale over which it adjusts suggests that the response to anthropogenic forcing may be different in coupled ocean-atmosphere climate models that parameterize and resolve mesoscale eddies.

Improved predictability of the troposphere using stratospheric final warmings

The final warming of the stratospheric polar vortex at the end of northern hemisphere winter is examined in ECMWF ERA-Interim reanalysis data and an ensemble of chemistry climate models, using 20 years of data from each. In some years the final warming is found to occur first in the mid-stratosphere, and in others to occur first in the upper stratosphere. The strength of the winter stratospheric polar vortex, refraction of planetary waves, and the altitudes at which the planetary waves break in the northern extratropics lead to this difference in the vertical profile of the final warming. Years in which the final warming occurs first in the mid-stratosphere show, on average, a more negative NAO pattern in April mean sea level pressure than years in which the warming occurs first in the upper stratosphere. Thus, in the northern hemisphere, additional predictive skill of tropospheric climate in April can be gained from a knowledge of the vertical profile of the stratospheric final warming.

Multimodel estimate of the global terrestrial water balance: setup and first results

Six land surface models and five global hydrological models participate in a model intercomparison project (WaterMIP), which for the first time compares simulation results of these different classes of models in a consistent way. In this paper the simulation setup is described and aspects of the multi-model global terrestrial water balance are presented. All models were run at 0.5 degree spatial resolution for the global land areas for a 15-year period (1985-1999) using a newly-developed global meteorological dataset. Simulated global terrestrial evapotranspiration, excluding Greenland and Antarctica, ranges from 415 to 586 mm year-1 (60,000 to 85,000 km3 year-1) and simulated runoff ranges from 290 to 457 mm year-1 (42,000 to 66,000 km3 year-1). Both the mean and median runoff fractions for the land surface models are lower than those of the global hydrological models, although the range is wider. Significant simulation differences between land surface and global hydrological models are found to be caused by the snow scheme employed. The physically-based energy balance approach used by land surface models generally results in lower snow water equivalent values than the conceptual degree-day approach used by global hydrological models. Some differences in simulated runoff and evapotranspiration are explained by model parameterizations, although the processes included and parameterizations used are not distinct to either land surface models or global hydrological models. The results show that differences between model are major sources of uncertainty. Climate change impact studies thus need to use not only multiple climate models, but also some other measure of uncertainty, (e.g. multiple impact models).

What influence will future solar activity changes over the 21st century have on projected global near-surface temperature changes?

During the 20th century, solar activity increased in magnitude to a so-called grand maximum. It is probable that this high level of solar activity is at or near its end. It is of great interest whether any future reduction in solar activity could have a significant impact on climate that could partially offset the projected anthropogenic warming. Observations and reconstructions of solar activity over the last 9000 years are used as a constraint on possible future variations to produce probability distributions of total solar irradiance over the next 100 years. Using this information, with a simple climate model, we present results of the potential implications for future projections of climate on decadal to multidecadal timescales. Using one of the most recent reconstructions of historic total solar irradiance, the likely reduction in the warming by 2100 is found to be between 0.06 and 0.1 K, a very small fraction of the projected anthropogenic warming. However, if past total solar irradiance variations are larger and climate models substantially underestimate the response to solar variations, then there is a potential for a reduction in solar activity to mitigate a small proportion of the future warming, a scenario we cannot totally rule out. While the Sun is not expected to provide substantial delays in the time to reach critical temperature thresholds, any small delays it might provide are likely to be greater for lower anthropogenic emissions scenarios than for higher-emissions scenarios.

Toward understanding of differences in current cloud retrievals of ARM ground-based measurements

Accurate observations of cloud microphysical properties are needed for evaluating and improving the representation of cloud processes in climate models and better estimate of the Earth radiative budget. However, large differences are found in current cloud products retrieved from ground-based remote sensing measurements using various retrieval algorithms. Understanding the differences is an important step to address uncertainties in the cloud retrievals. In this study, an in-depth analysis of nine existing ground-based cloud retrievals using ARM remote sensing measurements is carried out. We place emphasis on boundary layer overcast clouds and high level ice clouds, which are the focus of many current retrieval development efforts due to their radiative importance and relatively simple structure. Large systematic discrepancies in cloud microphysical properties are found in these two types of clouds among the nine cloud retrieval products, particularly for the cloud liquid and ice particle effective radius. Note that the differences among some retrieval products are even larger than the prescribed uncertainties reported by the retrieval algorithm developers. It is shown that most of these large differences have their roots in the retrieval theoretical bases, assumptions, as well as input and constraint parameters. This study suggests the need to further validate current retrieval theories and assumptions and even the development of new retrieval algorithms with more observations under different cloud regimes.

Multimodel assessment of the upper troposphere and lower stratosphere: Extratropics

A multimodel assessment of the performance of chemistry-climate models (CCMs) in the extratropical upper troposphere/lower stratosphere (UTLS) is conducted for the first time. Process-oriented diagnostics are used to validate dynamical and transport characteristics of 18 CCMs using meteorological analyses and aircraft and satellite observations. The main dynamical and chemical climatological characteristics of the extratropical UTLS are generally well represented by the models, despite the limited horizontal and vertical resolution. The seasonal cycle of lowermost stratospheric mass is realistic, however with a wide spread in its mean value. A tropopause inversion layer is present in most models, although the maximum in static stability is located too high above the tropopause and is somewhat too weak, as expected from limited model resolution. Similar comments apply to the extratropical tropopause transition layer. The seasonality in lower stratospheric chemical tracers is consistent with the seasonality in the Brewer-Dobson circulation. Both vertical and meridional tracer gradients are of similar strength to those found in observations. Models that perform less well tend to use a semi-Lagrangian transport scheme and/or have a very low resolution. Two models, and the multimodel mean, score consistently well on all diagnostics, while seven other models score well on all diagnostics except the seasonal cycle of water vapor. Only four of the models are consistently below average. The lack of tropospheric chemistry in most models limits their evaluation in the upper troposphere. Finally, the UTLS is relatively sparsely sampled by observations, limiting our ability to quantitatively evaluate many aspects of model performance.

Downscaling from GCM precipitation: a benchmark for dynamical and statistical downscaling methods

A precipitation downscaling method is presented using precipitation from a general circulation model (GCM) as predictor. The method extends a previous method from monthly to daily temporal resolution. The simplest form of the method corrects for biases in wet-day frequency and intensity. A more sophisticated variant also takes account of flow-dependent biases in the GCM. The method is flexible and simple to implement. It is proposed here as a correction of GCM output for applications where sophisticated methods are not available, or as a benchmark for the evaluation of other downscaling methods. Applied to output from reanalyses (ECMWF, NCEP) in the region of the European Alps, the method is capable of reducing large biases in the precipitation frequency distribution, even for high quantiles. The two variants exhibit similar performances, but the ideal choice of method can depend on the GCM/reanalysis and it is recommended to test the methods in each case. Limitations of the method are found in small areas with unresolved topographic detail that influence higher-order statistics (e.g. high quantiles). When used as benchmark for three regional climate models (RCMs), the corrected reanalysis and the RCMs perform similarly in many regions, but the added value of the latter is evident for high quantiles in some small regions.

Comparison of different boundary layer surface schemes using single point micrometeorological field data

 In the last decade, a vast number of land surface schemes has been designed for use in global climate models, atmospheric weather prediction, mesoscale numerical models, ecological models, and models of global changes. Since land surface schemes are designed for different purposes they have various levels of complexity in the treatment of bare soil processes, vegetation, and soil water movement. This paper is a contribution to a little group of papers dealing with intercomparison of differently designed and oriented land surface schemes. For that purpose we have chosen three schemes for classification: i) global climate models, BATS (Dickinson et al., 1986; Dickinson et al., 1992); ii) mesoscale and ecological models, LEAF (Lee, 1992) and iii) mesoscale models, LAPS (Mihailović, 1996; Mihailović and Kallos, 1997; Mihailović et al., 1999) according to the Shao et al. (1995) classification. These schemes were compared using surface fluxes and leaf temperature outputs obtained by time integrations of data sets derived from the micrometeorological measurements above a maize field at an experimental site in De Sinderhoeve (The Netherlands) for 18 August, 8 September, and 4 October 1988. Finally, comparison of the schemes was supported applying a simple statistical analysis on the surface flux outputs.