Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

Standardised ileal digestibility of crude protein and amino acids of UK-grown peas and faba beans by broilers

In view of the increasing interest in home-grown legumes as components of diets for non-ruminant livestock and in an attempt to reduce the reliance on imported soya bean meal (SBM), two experiments were conducted to evaluate samples of peas and faba beans for their standardised ileal digestibility (SID) of amino acids determined with young broiler chicks. Experiment 1 evaluated six faba bean and seven pea cultivars and Experiment 2 evaluated two faba bean and three pea cultivars as well as a sample of soya bean meal provided as a reference material. Peas and beans were added at 750g/kg as the only source of protein/amino acids in a semi-synthetic diet containing the inert marker titanium dioxide; SBM was added, in a control diet, at 500g/kg. Each diet was fed to six replicates of a cage containing two Ross-type broilers for 96h at which point birds were culled allowing removal of ileal digesta. Chemical analyses allowed the calculation of the coefficient of SID of amino acids. There were no differences between samples of the same pulse species (P>0.05) but peas had higher values (P<0.05), similar to SBM, than beans. Trypsin inhibitor content (expressed as g trypsin inhibitor units/mg sample) of all pea samples was low and in the range 0.83–1.77mg/kg. There was relatively little variation in bean tannin content and composition amongst the coloured-flowered varieties; however, the white-flowered cultivar had no tannins. There was no correlation between tannin content and coefficient of SID. The content of SID of amino acids (g/kg legume) was higher in SBM when compared with peas and beans by virtue of having higher total concentrations.

Canopy characteristics of contrasting clones of cacao (Theobroma cacao)

Canopy characteristics (leaf area index, fractional light interception, extinction coefficient) of mature trees of ten clonally propagated cacao cultivars were measured over a period of 14 months at an experimental site in Bahia, Brazil. Differences in leaf area index between clones became more pronounced over time. When an approximately constant leaf area index was reached (after about nine months), LAI varied between clones from 2.8 to 4.5. Clonal differences in the relationship between leaf area index and fractional light interception implied differences in canopy architecture, as reflected by the range of extinction coefficients (mean values ranged from 0.63 for the clone TSH-565 to 0.82 for CC-10). The results demonstrate the potential for breeding more photosynthetically efficient cacao canopies.

Assessment of wheat cultivars for drought tolerance via osmotic stress imposed at early seedling growth stages

A study was conducted in the Department of Plant Breeding and Genetics,Sindh Agriculture University, Tandojam, Pakistan during the year 2009. Sixteen spring wheat cultivars (Triticum aestivum L.) were screened under osmotic stress with three treatments i.e. control-no PEG (polyethylene glycol), 15 percent and 25 percent PEG-6000 solution. The analysis of variance indicated significant differences among treatments for all seedling traits except seed germination percentage. Varieties also differed significantly in germination percentage, coleoptile length, shoot root length, shoot weight, root/shoot ratio and seed vigour index. However, shoot and root weights were non-significant. Significant interactions revealed that cultivars responded variably to osmotic stress treatments; hence provided better opportunity to select drought tolerant cultivars at seedling growth stages. The relative decrease over averages due to osmotic stress was 0.8 percent in seed germination, 53 percent in coleoptile length 62.9 percent in shoot length, 74.4 percent in root length, 50.6 percent in shoot weight, 45.1 percent in root weight, 30.2 percent in root/shoot ratio and 68.5 percent in seed vigour index. However, relative decrease of individual variety for various seedling traits could be more meaningful which indicated that cultivar TD-1 showed no reduction in coleoptile length, while minimum decline was noted in Anmol. For shoot length, cultivar Sarsabz expressed minimum reduction followed by Anmol. However, cultivars Anmol, Moomal, Inqalab-91, and Pavan gave almost equally lower reductions for root length suggesting their higher stress tolerance. In other words, cultivars Anmol, Moomal, Inqalab-91, Sarsabz, TD-1, ZA-77 and Pavan had relatively longer coleoptiles, shoots and roots, and were regarded as drought tolerant. Correlation coefficients among seedlings traits were significant and positive for all traits except germination percentage which had no significant correlation with any of other trait. The results indicated that increase in one trait may cause simultaneous increase in other traits; hence selection for any of these seedling attributes will lead to develop drought tolerant wheat cultivars.

Regulation of surface water quality in a Cretaceous chalk catchment, UK: an assessment of the relative importance of instream and wetland processes

To investigate the relative importance of instream nutrient spiralling and wetland transformation processes on surface water quality, total nitrogen (TN) and total phosphorus (TP) concentrations in a 200 m reach of the River Lambourn in the south-east of England were monitored over a 2-year period. In addition, the soil pore water nutrient dynamics in a riparian ecosystem adjacent to the river were investigated. Analysis of variance indicated that TN, TP and suspended sediment concentrations recorded upstream of the wetland were statistically significantly higher (P<0.05) than those downstream of the site. Such results suggest that the wetland was performing a nutrient retention function. Indeed, analysis of soil pore waters within the site show that up to 85% of TN and 70% of TP was removed from water flowing through the wetland during baseflow conditions, thus supporting the theory that the wetland played an important role in the regulation of surface water quality at the site. However, the small variations observed (0.034 mg TN l-1 and 0.031 mg P l-1) are consistent with the theory of nutrient spiralling suggesting that both instream and wetland retention processes have a causal effect on surface water quality.

Concentrations of free amino acids and sugars in nine potato varieties: effects of storage and relationship with acrylamide formation

Acrylamide forms during cooking and processing predominately from the reaction of free asparagine and reducing sugars in the Maillard reaction. The identification of low free asparagine and reducing sugar varieties of crops is therefore an important target. In this study, nine varieties of potato (French fry varieties Maris Piper (from two suppliers), Pentland Dell, King Edward, Daisy, and Markies; and chipping varieties Lady Claire, Lady Rosetta, Saturna, and Hermes) grown in the United Kingdom in 2009 were analyzed at monthly intervals through storage from November 2009 to July 2010. Acrylamide formation was measured in heated flour and chips fried in oil. Analysis of variance revealed significant interactions between varieties nested within type (French fry and chipping) and storage time for most free amino acids, glucose, fructose, and acrylamide formation. Acrylamide formed in chips correlated significantly with acrylamide formed in flour and with chip color. There were significant correlations between glucose or total reducing sugar concentration and acrylamide formation in both variety types, but with fructose the correlation was much stronger for chipping than for French fry varieties. Conversely, there were significant correlations with acrylamide formation for both total free amino acid and free asparagine concentration in the French fry but not chipping varieties. The study showed the potential of variety selection for preventing unacceptable levels of acrylamide formation in potato products and the variety-dependent effect of long-term storage on acrylamide risk. It also highlighted the complex relationship between precursor concentration and acrylamide risk in potatoes.

Extending Murty interferometry to the Terahertz part of the spectrum

We discuss some novel technologies that enable the implementation of shearing interferometry at the terahertz part of the spectrum. Possible applications include the direct measurement of lens parameters, the measurement of refractive index of materials that are transparent to terahertz frequencies, determination of homogeneity of samples, measurement of optical distortions and the non-contact evaluation of thermal expansion coefficient of materials buried inside media that are opaque to optical or infrared frequencies but transparent to THz frequencies. The introduction of a shear to a Gaussian free-space propagating terahertz beam in a controlled manner also makes possible a range of new encoding and optical signal processing modalities.

Changes in tropical Atlantic interannual variability from a substantial weakening of the meridional overturning circulation

In response to a substantial weakening of the Atlantic Meridional Overturning Circulation (AMOC)— from a coupled ocean–atmosphere general circulation model experiment—significant changes in the interannual variability are found over the tropical Atlantic, characterized by an increase of variance (by ~150 %) in boreal late spring-early summer and a decrease of variance (by ~60 %) in boreal autumn. This study focuses on understanding physical mechanisms responsible for these changes in interannual variability in the tropical Atlantic. It demonstrates that the increase of variability in spring is a consequence of an increase in the variance of the El Niño-Southern Oscillation, which has a large impact on the tropical Atlantic via anomalous surface heat fluxes. Winter El Niño (La Niña) affects the eastern equatorial Atlantic by decreasing (increasing) cloud cover and surface wind speed which is associated with anomalous downward (upward) short wave radiation and reduced (enhanced) upward latent heat fluxes, creating anomalous positive (negative) sea surface temperature (SST) anomalies over the region from winter to spring. On the other hand, the decrease of SST variance in autumn is due to a deeper mean thermocline which weakens the impact of the thermocline movement on SST variation. The comparison between the model results and observations is not straightforward owing to the influence of model biases and the lack of a major MOC weakening event in the instrumental record. However, it is argued that the basic physical mechanisms found in the model simulations are likely to be robust and therefore have relevance to understanding tropical Atlantic variability in the real world, perhaps with modified seasonality.

The global distribution of phytoplankton size spectrum and size classes from their light-absorption spectra derived from satellite data

The absorption spectra of phytoplankton in the visible domain hold implicit information on the phytoplankton community structure. Here we use this information to retrieve quantitative information on phytoplankton size structure by developing a novel method to compute the exponent of an assumed power-law for their particle-size spectrum. This quantity, in combination with total chlorophyll-a concentration, can be used to estimate the fractional concentration of chlorophyll in any arbitrarily-defined size class of phytoplankton. We further define and derive expressions for two distinct measures of cell size of mixed populations, namely, the average spherical diameter of a bio-optically equivalent homogeneous population of cells of equal size, and the average equivalent spherical diameter of a population of cells that follow a power-law particle-size distribution. The method relies on measurements of two quantities of a phytoplankton sample: the concentration of chlorophyll-a, which is an operational index of phytoplankton biomass, and the total absorption coefficient of phytoplankton in the red peak of visible spectrum at 676 nm. A sensitivity analysis confirms that the relative errors in the estimates of the exponent of particle size spectra are reasonably low. The exponents of phytoplankton size spectra, estimated for a large set of in situ data from a variety of oceanic environments (~ 2400 samples), are within a reasonable range; and the estimated fractions of chlorophyll in pico-, nano- and micro-phytoplankton are generally consistent with those obtained by an independent, indirect method based on diagnostic pigments determined using high-performance liquid chromatography. The estimates of cell size for in situ samples dominated by different phytoplankton types (diatoms, prymnesiophytes, Prochlorococcus, other cyanobacteria and green algae) yield nominal sizes consistent with the taxonomic classification. To estimate the same quantities from satellite-derived ocean-colour data, we combine our method with algorithms for obtaining inherent optical properties from remote sensing. The spatial distribution of the size-spectrum exponent and the chlorophyll fractions of pico-, nano- and micro-phytoplankton estimated from satellite remote sensing are in agreement with the current understanding of the biogeography of phytoplankton functional types in the global oceans. This study contributes to our understanding of the distribution and time evolution of phytoplankton size structure in the global oceans.

Retrieval of phytoplankton size from bio-optical measurements: theory and applications

The absorption coefficient of a substance distributed as discrete particles in suspension is less than that of the same material dissolved uniformly in a medium—a phenomenon commonly referred to as the flattening effect. The decrease in the absorption coefficient owing to flattening effect depends on the concentration of the absorbing pigment inside the particle, the specific absorption coefficient of the pigment within the particle, and on the diameter of the particle, if the particles are assumed to be spherical. For phytoplankton cells in the ocean, with diameters ranging from less than 1 µm to more than 100 µm, the flattening effect is variable, and sometimes pronounced, as has been well documented in the literature. Here, we demonstrate how the in vivo absorption coefficient of phytoplankton cells per unit concentration of its major pigment, chlorophyll a, can be used to determine the average cell size of the phytoplankton population. Sensitivity analyses are carried out to evaluate the errors in the estimated diameter owing to potential errors in the model assumptions. Cell sizes computed for field samples using the model are compared qualitatively with indirect estimates of size classes derived from high performance liquid chromatography data. Also, the results are compared quantitatively against measurements of cell size in laboratory cultures. The method developed is easy-to-apply as an operational tool for in situ observations, and has the potential for application to remote sensing of ocean colour data.

Estimates of global multicomponent aerosol optical depth and direct radiative perturbation in the Laboratoire de Météorologie Dynamique general circulation model

The global cycle of multicomponent aerosols including sulfate, black carbon (BC),organic matter (OM), mineral dust, and sea salt is simulated in the Laboratoire de Me´te´orologie Dynamique general circulation model (LMDZT GCM). The seasonal open biomass burning emissions for simulation years 2000–2001 are scaled from climatological emissions in proportion to satellite detected fire counts. The emissions of dust and sea salt are parameterized online in the model. The comparison of model-predicted monthly mean aerosol optical depth (AOD) at 500 nm with Aerosol Robotic Network (AERONET) shows good agreement with a correlation coefficient of 0.57(N = 1324) and 76% of data points falling within a factor of 2 deviation. The correlation coefficient for daily mean values drops to 0.49 (N = 23,680). The absorption AOD (ta at 670 nm) estimated in the model is poorly correlated with measurements (r = 0.27, N = 349). It is biased low by 24% as compared to AERONET. The model reproduces the prominent features in the monthly mean AOD retrievals from Moderate Resolution Imaging Spectroradiometer (MODIS). The agreement between the model and MODIS is better over source and outflow regions (i.e., within a factor of 2).There is an underestimation of the model by up to a factor of 3 to 5 over some remote oceans. The largest contribution to global annual average AOD (0.12 at 550 nm) is from sulfate (0.043 or 35%), followed by sea salt (0.027 or 23%), dust (0.026 or 22%),OM (0.021 or 17%), and BC (0.004 or 3%). The atmospheric aerosol absorption is predominantly contributed by BC and is about 3% of the total AOD. The globally and annually averaged shortwave (SW) direct aerosol radiative perturbation (DARP) in clear-sky conditions is �2.17 Wm�2 and is about a factor of 2 larger than in all-sky conditions (�1.04 Wm�2). The net DARP (SW + LW) by all aerosols is �1.46 and �0.59 Wm�2 in clear- and all-sky conditions, respectively. Use of realistic, less absorbing in SW, optical properties for dust results in negative forcing over the dust-dominated regions.

Method of determining a geophysical-scale sea ice rheology from laboratory measurements

We present a methodology that allows a sea ice rheology, suitable for use in a General Circulation Model (GCM), to be determined from laboratory and tank experiments on sea ice when combined with a kinematic model of deformation. The laboratory experiments determine a material rheology for sea ice, and would investigate a nonlinear friction law of the form τ ∝ σ n⅔, instead of the more familiar Amonton's law, τ = μσn (τ is the shear stress, μ is the coefficient of friction and σ n is the normal stress). The modelling approach considers a representative region R containing ice floes (or floe aggregates), separated by flaws. The deformation of R is imposed and the motion of the floes determined using a kinematic model, which will be motivated from SAR observations. Deformation of the flaws is inferred from the floe motion and stress determined from the material rheology. The stress over R is then determined from the area-weighted contribution from flaws and floes

Construction of neurofuzzy models for imbalanced data classification

We propose a new class of neurofuzzy construction algorithms with the aim of maximizing generalization capability specifically for imbalanced data classification problems based on leave-one-out (LOO) cross validation. The algorithms are in two stages, first an initial rule base is constructed based on estimating the Gaussian mixture model with analysis of variance decomposition from input data; the second stage carries out the joint weighted least squares parameter estimation and rule selection using orthogonal forward subspace selection (OFSS)procedure. We show how different LOO based rule selection criteria can be incorporated with OFSS, and advocate either maximizing the leave-one-out area under curve of the receiver operating characteristics, or maximizing the leave-one-out Fmeasure if the data sets exhibit imbalanced class distribution. Extensive comparative simulations illustrate the effectiveness of the proposed algorithms.

Ozonolysis of methyl oleate monolayers at the air–water interface: oxidation kinetics, reaction products and atmospheric implications

Ozonolysis of methyl oleate monolayers at the air–water interface results in surprisingly rapid loss of material through cleavage of the C[double bond, length as m-dash]C bond and evaporation/dissolution of reaction products. We determine using neutron reflectometry a rate coefficient of (5.7 ± 0.9) × 10−10 cm2 molecule−1 s−1 and an uptake coefficient of [similar]3 × 10−5 for the oxidation of a methyl ester monolayer: the atmospheric lifetime is [similar]10 min. We obtained direct experimental evidence that <2% of organic material remains at the surface on atmospheric timescales. Therefore known long atmospheric residence times of unsaturated fatty acids suggest that these molecules cannot be present at the interface throughout their ageing cycle, i.e. the reported atmospheric longevity is likely to be attributed to presence in the bulk and viscosity-limited reactive loss. Possible reaction products were characterized by ellipsometry and uncertainties in the atmospheric fate of organic surfactants such as oleic acid and its methyl ester are discussed. Our results suggest that a minor change to the structure of the molecule (fatty acid vs. its methyl ester) considerably impacts on reactivity and fate of the organic film.

Solar causes of the long-term increase in geomagnetic activity

We analyze the causes of the century-long increase in geomagnetic activity, quantified by annual means of the aa index, using observations of interplanetary space, galactic cosmic rays, the ionosphere, and the auroral electrojet, made during the last three solar cycles. The effects of changes in ionospheric conductivity, the Earth's dipole tilt, and magnetic moment are shown to be small; only changes in near-Earth interplanetary space make a significant contribution to the long-term increase in activity. We study the effects of the interplanetary medium by applying dimensional analysis to generate the optimum solar wind-magnetosphere energy coupling function, having an unprecedentedly high correlation coefficient of 0.97. Analysis of the terms of the coupling function shows that the largest contributions to the drift in activity over solar cycles 20-22 originate from rises in the average interplanetary magnetic field (IMF) strength, solar wind concentration, and speed; average IMF orientation has grown somewhat less propitious for causing geomagnetic activity. The combination of these factors explains almost all of the 39% rise in aa observed over the last three solar cycles. Whereas the IMF strength varies approximately in phase with sunspot numbers, neither its orientation nor the solar wind density shows any coherent solar cycle variation. The solar wind speed peaks strongly in the declining phase of even-numbered cycles and can be identified as the chief cause of the phase shift between the sunspot numbers and the aa index. The rise in the IMF magnitude, the largest single contributor to the drift in geomagnetic activity, is shown to be caused by a rise in the solar coronal magnetic field, consistent with a rise in the coronal source field, modeled from photospheric observations, and an observed decay in cosmic ray fluxes.