The hardness profile as a tool to detect spurious stationary points in the potential energy surface

The energy and hardness profile for a series of inter and intramolecular conformational changes at several levels of calculation were computed. The hardness profiles were found to be calculated as the difference between the vertical ionization potential and electron affinity. The hardness profile shows the correct number of stationary points independently of the basis set and methodology used. It was found that the hardness profiles can be used to check the reliability of the energy profiles for those chemical system

Evidence of heavy metal movement down the profile of a heavily-sludged soil

Two sites in central England where sewage sludge has been deposited for decades were studied to measure the heavy metal distribution in the soil profiles. The first site (S 1) was a field receiving heavy loads sludge from a nearby wastewater treatment plant, and the second (S2) was a farm applying 'normal' sludge rates of 8 t ha(-1) y(-1) of the same sludge. Soil samples were also taken by a near-by untreated control site. In S I the movement of heavy metals was significant even down to 80 cm depth compared to the control. In S2, the concentrations of lead (Pb) and zinc (Zn) and the organic matter content were higher than the control down to 20 cm, while nickel (Ni) moved significantly down to 80 cm. This underlies. the possibility that the metals bound onto organic surfaces moved along with organic matter down to that depth. The movement of metals in S2 points out the potential risks of applying sewage sludge for a long time.

Calcrete profile development in quaternary alluvial sequences, southeast Spain: Implications for using calcretes as a basis for landform chronologies

A detailed study of the morphology and micro-morphology of Quaternary alluvial calcrete profiles from the Sorbas Basin shows that calcretes may be morphologically simple or complex. The 'simple' profiles reflect pedogenesis occurring after alluvial terrace formation and consist of a single pedogenic horizon near the land surface. The 'complex' profiles reflect the occurrence of multiple calcrete events during terrace sediment aggradation and further periods of pedogenesis after terrace formation. These 'complex' calcrete profiles are consequently described as composite profiles. The exact morphology of the composite profiles depends upon: (1) the number of calcrete-forming events occurring during terrace sediment aggradation; (2) the amount of sediment accretion that occurs between each period of calcrete formation; and (3) the degree of pedogenesis after terrace formation. Simple calcrete profiles are most useful in establishing landform chronologies because they represent a single phase of pedogenesis after terrace formation. Composite profiles are more problematic. Pedogenic calcretes that form within them may inherit carbonate from calcrete horizons occurring lower down in the terrace sediments. In addition erosion may lead to the exhumation of older calcretes within the terrace sediment. Calcrete 'inheritance' may make pedogenic horizons appear more mature than they actually are and produce horizons containing carbonate embracing a range of ages. Calcrete exhumation exposes calcrete horizons whose morphology and radiometric ages are wholly unrelated to terrace surface age. Composite profiles are, therefore, only suitable for chronological studies if the pedogenic horizon capping the terrace sequence can be clearly distinguished from earlier calcrete-forming events. Thus, a detailed morphological/micro-morphological study is required before any chronological study is undertaken. This is the only way to establish whether particular calcrete profiles are suitable for dating purposes. Copyright (C) 2003 John Wiley Sons, Ltd.

City Profile: Havana

Since 1989, after 40 years of curbing urban development and under-investment in urban infrastructure, Havana is slowly regaining its primacy as Cuba's, and indeed one of the Caribbean's. major tourist destinations. This profile focuses on the urban change undergone by Havana since the introduction of the socalled'Special Period' in 1.989, following the collapse of State socialism in the USSR and Eastern Europe. A particular emphasis is placed on the role played by international tourism as a catalyst for socio-economic and environmental change in Havana in the 1990s. The profile also reviews the main urban development and governance issues that Havana is likely to face in the future. (c) 2005 Elsevier Ltd. All rights reserved.

Estimating detailed soil water profile records from point measurements

Temporal and spatial patterns of soil water content affect many soil processes including evaporation, infiltration, ground water recharge, erosion and vegetation distribution. This paper describes the analysis of a soil moisture dataset comprising a combination of continuous time series of measurements at a few depths and locations, and occasional roving measurements at a large number of depths and locations. The objectives of the paper are: (i) to develop a technique for combining continuous measurements of soil water contents at a limited number of depths within a soil profile with occasional measurements at a large number of depths, to enable accurate estimation of the soil moisture vertical pattern and the integrated profile water content; and (ii) to estimate time series of soil moisture content at locations where there are just occasional soil water measurements available and some continuous records from nearby locations. The vertical interpolation technique presented here can strongly reduce errors in the estimation of profile soil water and its changes with time. On the other hand, the temporal interpolation technique is tested for different sampling strategies in space and time, and the errors generated in each case are compared.

The effect of consumption volume on profile and liking of oral nutritional supplements of varied sweetness: sequential profiling and boredom tests

Oral nutrition supplements (ONS) are routinely prescribed to those with, or at risk of, malnutrition. Previous research identified poor compliance due to taste and sweetness. This paper investigates taste and hedonic liking of ONS, of varying sweetness and metallic levels, over consumption volume; an important consideration as patients are prescribed large volumes of ONS daily. A sequential descriptive profile was developed to determine the perception of sensory attributes over repeat consumption of ONS. Changes in liking of ONS following repeat consumption were characterised by a boredom test. Certain flavour (metallic taste, soya milk flavour) and mouthfeel (mouthdrying, mouthcoating) attributes built up over increased consumption volume (p 0.002). Hedonic liking data from two cohorts, healthy older volunteers (n = 32, median age 73) and patients (n = 28, median age 85), suggested such build-up was disliked. Efforts made to improve the palatability of ONS must take account of the build up of taste and mouthfeel characteristics over increased consumption volume.

Enhancement of the aerosol direct radiative effect by semi-volatile aerosol components: airborne measurements in North-Western Europe

A case study of atmospheric aerosol measurements exploring the impact of the vertical distribution of aerosol chemical composition upon the radiative budget in North-Western Europe is presented. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) on both an airborne platform and a ground-based site at Cabauw in the Netherlands. The examined period in May 2008 was characterised by enhanced pollution loadings in North-Western Europe and was dominated by ammonium nitrate and Organic Matter (OM). Both ammonium nitrate and OM were observed to increase with altitude in the atmospheric boundary layer. This is primarily attributed to partitioning of semi-volatile gas phase species to the particle phase at reduced temperature and enhanced relative humidity. Increased ammonium nitrate concentrations in particular were found to strongly increase the ambient scattering potential of the aerosol burden, which was a consequence of the large amount of associated water as well as the enhanced mass. During particularly polluted conditions, increases in aerosol optical depth of 50–100% were estimated to occur due to the observed increase in secondary aerosol mass and associated water uptake. Furthermore, the single scattering albedo was also shown to increase with height in the boundary layer. These enhancements combined to increase the negative direct aerosol radiative forcing by close to a factor of two at the median percentile level. Such increases have major ramifications for regional climate predictions as semi-volatile components are often not included in aerosol models. The results presented here provide an ideal opportunity to test regional and global representations of both the aerosol vertical distribution and subsequent impacts in North-Western Europe. North-Western Europe can be viewed as an analogue for the possible future air quality over other polluted regions of the Northern Hemisphere, where substantial reductions in sulphur dioxide emissions have yet to occur. Anticipated reductions in sulphur dioxide in polluted regions will result in an increase in the availability of ammonia to form ammonium nitrate as opposed to ammonium sulphate. This will be most important where intensive agricultural practises occur. Our observations over North-Western Europe, a region where sulphur dioxide emissions have already been reduced, indicate that failure to include the semi-volatile behaviour of ammonium nitrate will result in significant errors in predicted aerosol direct radiative forcing. Such errors will be particularly significant on regional scales.

A well-characterised peak identification list of MALDI MS profile peaks for human blood serum

MALDI MS profiling, using easily available body fluids such as blood serum, has attracted considerable interest for its potential in clinical applications. Despite the numerous reports on MALDI MS profiling of human serum, there is only scarce information on the identity of the species making up these profiles, particularly in the mass range of larger peptides. Here, we provide a list of more than 90 entries of MALDI MS profile peak identities up to 10 kDa obtained from human blood serum. Various modifications such as phosphorylation were detected among the peptide identifications. The overlap with the few other MALDI MS peak lists published so far was found to be limited and hence our list significantly extends the number of identified peaks commonly found in MALDI MS profiling of human blood serum.

Estimation of the stoichiometry of volatile fatty acid production in the rumen of lactating cows

The purpose of this study was to improve the prediction of the quantity and type of Volatile Fatty Acids (VFA) produced from fermented substrate in the rumen of lactating cows. A model was formulated that describes the conversion of substrate (soluble carbohydrates, starch, hemi-cellulose, cellulose, and protein) into VFA (acetate, propionate, butyrate, and other VFA). Inputs to the model were observed rates of true rumen digestion of substrates, whereas outputs were observed molar proportions of VFA in rumen fluid. A literature survey generated data of 182 diets (96 roughage and 86 concentrate diets). Coefficient values that define the conversion of a specific substrate into VFA were estimated meta-analytically by regression of the model against observed VFA molar proportions using non-linear regression techniques. Coefficient estimates significantly differed for acetate and propionate production in particular, between different types of substrate and between roughage and concentrate diets. Deviations of fitted from observed VFA molar proportions could be attributed to random error for 100%. In addition to regression against observed data, simulation studies were performed to investigate the potential of the estimation method. Fitted coefficient estimates from simulated data sets appeared accurate, as well as fitted rates of VFA production, although the model accounted for only a small fraction (maximally 45%) of the variation in VFA molar proportions. The simulation results showed that the latter result was merely a consequence of the statistical analysis chosen and should not be interpreted as an indication of inaccuracy of coefficient estimates. Deviations between fitted and observed values corresponded to those obtained in simulations. (c) 2005 Elsevier Ltd. All rights reserved.

Technical note: A proposed method to determine the extent of degradation of a feed in the rumen from the degradation profile obtained with the in vitro gas production technique using feces as the inoculum

A method is proposed to determine the extent of degradation in the rumen involving a two-stage mathematical modeling process. In the first stage, a statistical model shifts (or maps) the gas accumulation profile obtained using a fecal inoculum to a ruminal gas profile. Then, a kinetic model determines the extent of degradation in the rumen from the shifted profile. The kinetic model is presented as a generalized mathematical function, allowing any one of a number of alternative equation forms to be selected. This method might allow the gas production technique to become an approach for determining extent of degradation in the rumen, decreasing the need for surgically modified animals while still maintaining the link with the animal. Further research is needed before the proposed methodology can be used as a standard method across a range of feeds.