Assessment of the consistency of near-infrared water vapor line intensities using high-spectral-resolution ground-based Fourier transform measurements of solar radiation

Calculations of the absorption of solar radiation by atmospheric gases, and water vapor in particular, are dependent on the quality of databases of spectral line parameters. There has been increasing scrutiny of databases such as HITRAN in recent years, but this has mostly been performed on a band-by-band basis. We report nine high-spectral-resolution (0.03 cm(-1)) measurements of the solar radiation reaching the surface in southern England over the wave number range 2000 to 12,500 cm(-1) (0.8 to 5 mm) that allow a unique assessment of the consistency of the spectral line databases over this entire spectral region. The data are assessed in terms of the modeled water vapor column that is required to bring calculations and observations into agreement; for an entirely consistent database, this water vapor column should be constant with frequency. For the HITRAN01 database, the spread in water vapor column is about 11%, with distinct shifts between different spectral regions. The HITRAN04 database is in significantly better agreement (about 5% spread) in the completely updated 3000 to 8000 cm(-1) spectral region, but inconsistencies between individual spectral regions remain: for example, in the 8000 to 9500 cm(-1) spectral region, the results indicate an 18% (+/- 1%) underestimate in line intensities with respect to the 3000 to 8000 cm(-1) region. These measurements also indicate the impact of isotopic fractionation of water vapor in the 2500 to 2900 cm(-1) range, where HDO lines dominate over the lines of the most abundant isotope of H2O.

The role of sketches in supporting near-synchronous remote communication in computer supported collaborative design

This paper presents recent research into the functions and value of sketch outputs during computer supported collaborative design. Sketches made primarily exploiting whiteboard technology are shown to support subjects engaged in remote collaborative design, particularly when constructed in ‘nearsynchronous’ communication. The authors define near-synchronous communication and speculate that it is compatible with the reflective and iterative nature of design activity. There appears to be significant similarities between the making of sketches in near-synchronous remote collaborative design and those made on paper in more traditional face-to-face settings With the current increase in the use of computer supported collaborative working (CSCW) in undergraduate and postgraduate design education it is proposed that sketches and sketching can make important contributions to design learning in this context

Solar induced climate effects

Solar electromagnetic radiation powers Earth’s climate system and, consequently, it is often naively assumed that changes in this solar output must be responsible for changes in Earth’s climate. However, the Sun is close to a blackbody radiator and so emits according to its surface temperature and the huge thermal time constant of the outer part of the Sun limits the variability in surface temperature and hence output. As a result, on all timescales of interest, changes in total power output are limited to small changes in effective surface temperature (associated with magnetic fields) and potential, although as yet undetected, solar radius variations. Larger variations are seen in the UV part of the spectrum which is emitted from the lower solar atmosphere (the chromosphere) and which influences Earth’s stratosphere. There is interest in“top-down” mechanisms whereby solar UV irradiance modulates stratospheric temperatures and winds which, in turn, may influence the underlying troposphere where Earth’s climate and weather reside. This contrasts with “bottom-up” effects in which the small total solar irradiance (dominated by the visible and near-IR) variations cause surface temperature changes which drive atmospheric circulations. In addition to these electromagnetic outputs, the Sun modulates energetic particle fluxes incident on the Earth. Solar Energetic Particles (SEP) are emitted by solar flares and from the shock fronts ahead of supersonic (and super-Alfvenic) ejections of material from the solar atmosphere. These SEPs enhance the destruction of polar stratospheric ozone which could be an additional form of top-down climate forcing. Even more energetic are Galactic Cosmic Rays (GCRs). These particles are not generated by the Sun, rather they originate at the shock fronts emanating from violent galactic events such as supernovae explosions; however, the expansion of the solar magnetic field into interplanetary space means that the Sun modulates the number of GCRs reaching Earth. These play a key role in enabling Earth’s global electric (thunderstorm) circuit and it has been proposed that they also modulate the formation of clouds. Both electromagnetic and corpuscular solar effects are known to vary over the solar magnetic cycle which is typically between 10 and 14 yrs in length (with an average close to 11 yrs). The solar magnetic field polarity at any one phase of one of these activity cycles is opposite to that at the same phase of the next cycle and this influences some phenomena, for example GCRs, which therefore show a 22 yr (“Hale”) cycle on average. Other phenomena, such as irradiance modulation, do not depend on the polarity of the magnetic field and so show only the basic 11-yr activity cycle. However, any effects on climate are much more significant for solar drifts over centennial timescales. This chapter discusses and evaluates potential effects on Earth’s climate system of variations in these solar inputs. Because of the great variety of proposed mechanisms, the wide range of timescales studied (from days to millennia) and the many debates (often triggered by the application of inadequate statistical methods), the literature on this subject is vast, complex, divergent and rapidly changing: consequently the number of references cited in this review is very large (yet still only a small fraction of the total).

The high-resolution infrared spectrum of HOF near 2700 cm-1: the ground and 2v2 states

The a/b hybrid-type ν1 fundamental and 2ν2 overtone bands of HOF were investigated by FTIR spectroscopy with a resolution close to 0.008 cm−1. Improved ground state parameters of HOF were determined from a merge of more than 3000 ground state combination differences formed from ν1 and previously measured ν2 transitions with the reported pure rotational lines. Excited state parameters of the v2 = 2 state, ν0 = 2686.924 6(1) and χ22 = −9.942 4(1) cm−1, were determined employing Watson's A-reduced Hamiltonian up to sixth order in I′ representation. The 2ν2 state was found to be unperturbed, the excited state parameters being closely related to those of ν2.

Developments in near infrared spectroscopy

Vibrational spectroscopy at high excitation is an important research frontier for two reasons. Firstly, the near infrared is proving to be an important area for the analytical applications of spectroscopy, and we would therefore like to understand how the spectra we observe relate to the molecular structure of the absorbing species. Secondly, there is a fundamental interest in understanding molecular dynamics and energy flow within a polyatomic molecule at high excitation, because this is the boundary between spectroscopy and chemistry through which we try to understand the details of a chemical reaction. In this presentation I shall survey recent progress in this field.

Introduction of 4-chloro-alpha-cyanocinnamic acid liquid matrices for high sensitivity UV-MALDI MS

Matrix-assisted laser desorption/ionization (MALDI) is a key ionization technique in mass spectrometry (MS) for the analysis of labile macromolecules. An important area of study and improvements in relation to MALDI and its application in high-sensitivity MS is that of matrix design and sample preparation. Recently, 4-chloro-alpha-cyanocinnamic acid (ClCCA) has been introduced as a new rationally designed matrix and reported to provide an improved analytical performance as demonstrated by an increase in sequence coverage of protein digests obtained by peptide mass mapping (PMM) (Jaskolla, T. W.; et al. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 12200-12205). This new matrix shows the potential to be a superior alternative to the commonly used and highly successful alpha-cyano-4-hydroxycinnamic acid (CHCA). We have taken this design one step further by developing and optimizing an ionic liquid matrix (ILM) and liquid support matrix (LSM) using ClCCA as the principle chromophore and MALDI matrix compound. These new liquid matrices possess greater sample homogeneity and a simpler morphology. The data obtained from our studies show improved sequence coverage for BSA digests compared to the traditional CHCA crystalline matrix and for the ClCCA-containing ILM a similar performance to the ClCCA crystalline matrix down to 1 fmol of BSA digest prepared in a single MALDI sample droplet with current sensitivity levels in the attomole range. The LSMs show a high tolerance to contamination such as ammonium bicarbonate, a commonly used buffering agent.

Whole crop cereals 2. Prediction of apparent digestibility and energy value from in vitro digestion techniques and near infrared reflectance spectroscopy and of chemical composition by near infrared reflectance spectroscopy

Samples of whole crop wheat (WCW, n = 134) and whole crop barley (WCB, n = 16) were collected from commercial farms in the UK over a 2-year period (2003/2004 and 2004/2005). Near infrared reflectance spectroscopy (NIRS) was compared with laboratory and in vitro digestibility measures to predict digestible organic matter in the dry matter (DOMD) and metabolisable energy (ME) contents measured in vivo using sheep. Spectral models using the mean spectra of two scans were compared with those using individual spectra (duplicate spectra). Overall NIRS accurately predicted the concentration of chemical components in whole crop cereals apart from crude protein. ammonia-nitrogen, water-soluble carbohydrates, fermentation acids and solubility values. In addition. the spectral models had higher prediction power for in vivo DOMD and ME than chemical components or in vitro digestion methods. Overall there Was a benefit from the use of duplicate spectra rather than mean spectra and this was especially so for predicting in vivo DOMD and ME where the sample population size was smaller. The spectral models derived deal equally well with WCW and WCB and Would he of considerable practical value allowing rapid determination of nutritive value of these forages before their use in diets of productive animals. (C) 2008 Elsevier B.V. All rights reserved.

Near infrared reflectance spectroscopy (NIRS) to predict biological parameters of maize silage: effects of particle comminution, oven drying temperature and the presence of residual moisture

Maize silage nutritive quality is routinely determined by near infrared reflectance spectroscopy (NIRS). However, little is known about the impact of sample preparation on the accuracy of the calibration to predict biological traits. A sample population of 48 maize silages representing a wide range of physiological maturities was used in a study to determine the impact of different sample preparation procedures (i.e., drying regimes; the presence or absence of residual moisture; the degree of particle comminution) on resultant NIR prediction statistics. All silages were scanned using a total of 12 combinations of sample pre-treatments. Each sample preparation combination was subjected to three multivariate regression techniques to give a total of 36 predictions per biological trait. Increased sample preparations procedure, relative to scanning the unprocessed whole plant (WP) material, always resulted in a numerical minimisation of model statistics. However, the ability of each of the treatments to significantly minimise the model statistics differed. Particle comminution was the most important factor, oven-drying regime was intermediate, and residual moisture presence was the least important. Models to predict various biological parameters of maize silage will be improved if material is subjected to a high degree of particle comminution (i.e., having been passed through a 1 mm screen) and developed on plant material previously dried at 60 degrees C. The extra effort in terms of time and cost required to remove sample residual moisture cannot be justified. (c) 2005 Elsevier B.V. All rights reserved.