Higher oxides of chlorine: absorption cross-sections of Cl2O6 and Cl2O4, the decomposition of Cl2O6, and the reactions of OClO with O and O-3

The absorption cross-sections of Cl2O6 and Cl2O4 have been obtained using a fast flow reactor with a diode array spectrometer (DAS) detection system. The absorption cross-sections at the wavelengths of maximum absorption (lambda(max)) determined in this study are those of Cl2O6: (1.47 +/- 0.15) x 10(-17) cm(2) molecule(-1), at lambda(max) = 276 nm and T = 298 K; and Cl2O4: (9.0 +/- 2.0) x 10(-19) cm(2) molecule(-1), at lambda(max) = 234 nm and T = 298 K. Errors quoted are two standard deviations together with estimates of the systematic error. The shapes of the absorption spectra were obtained over the wavelength range 200-450 nm for Cl2O6 and 200-350 nm for Cl2O4, and were normalized to the absolute cross-sections obtained at lambda(max) for each oxide, and are presented at 1 nm intervals. These data are discussed in relation to previous measurements. The reaction of O with OCIO has been investigated with the objective of observing transient spectroscopic absorptions. A transient absorption was seen, and the possibility is explored of identifying the species with the elusive sym-ClO3 or ClO4, both of which have been characterized in matrices, but not in the gas-phase. The photolysis of OCIO was also re-examined, with emphasis being placed on the products of reaction. UV absorptions attributable to one of the isomers of the ClO dimer, chloryl chloride (ClClO2) were observed; some Cl2O4 was also found at long photolysis times, when much of the ClClO2 had itself been photolysed. We suggest that reports of Cl2O6 formation in previous studies could be a consequence of a mistaken identification. At low temperatures, the photolysis of OCIO leads to the formation of Cl2O3 as a result of the addition of the ClO primary product to OCIO. ClClO2 also appears to be one product of the reaction between O-3 and OCIO, especially when the reaction occurs under explosive conditions. We studied the kinetics of the non-explosive process using a stopped-flow technique, and suggest a value for the room-temperature rate coefficient of (4.6 +/- 0.9) x 10(-19) cm(3) molecule(-1) s(-1) (limit quoted is 2sigma random errors). The photochemical and thermal decomposition of Cl2O6 is described in this paper. For photolysis at k = 254 nm, the removal of Cl2O6 is not accompanied by the build up of any other strong absorber. The implications of the results are either that the photolysis of Cl2O6 produces Cl-2 directly, or that the initial photofragments are converted rapidly to Cl-2. In the thermal decomposition of Cl2O6, Cl2O4 was shown to be a product of reaction, although not necessarily the major one. The kinetics of decomposition were investigated using the stopped-flow technique. At relatively high [OCIO] present in the system, the decay kinetics obeyed a first-order law, with a limiting first-order rate coefficient of 0.002 s(-1). (C) 2004 Elsevier B.V. All rights reserved.

A novel technique for differentiation of proteins in the development of acid gel structure from control and heat treated milk using confocal scanning laser microscopy

The incorporation of caseins and whey proteins into acid gels produced from unheated and heat treated skimmed milk was studied by confocal scanning laser microscopy (CSLM) using fluorescent labelled proteins. Bovine casein micelles were labelled using Alexa Fluor 594, while whey proteins were labelled using Alexa Fluor 488. Samples of the labelled protein solutions were introduced into aliquots of pasteurised skim milk, and skim milk heated to 90 degrees C for 2 min and 95 degrees C for 8 min. The milk was acidified at 40 degrees C to a final pH of 4.4 using 20 g gluconodelta-lactone/l (GDL). The formation of gels was observed with CSLM at two wavelengths (488 nm and 594 nm), and also by visual and rheological methods. In the control milk, as pH decreased distinct casein aggregates appeared, and as further pH reduction occurred, the whey proteins could be seen to coat the casein aggregates. With the heated milks, the gel structure was formed of continuous strands consisting of both casein and whey protein. The formation of the gel network was correlated with an increase in the elastic modulus for all three treatments, in relation to the severity of heat treatment. This model system allows the separate observation of the caseins and whey proteins, and the study of the interactions between the two protein fractions during the formation of the acid gel structure, on a real-time basis. The system could therefore be a valuable tool in the study of structure formation in yoghurt and other dairy protein systems.

Cooled infrared filters and dichroics for the James Webb Space Telescope Mid-Infrared Instrument

The cooled infrared filters and dichroic beam splitters manufactured for the Mid-Infrared Instrument are key optical components for the selection and isolation of wavelengths in the study of astrophysical properties of stars, galaxies, and other planetary objects. We describe the spectral design and manufacture of the precision cooled filter coatings for the spectrometer (7 K) and imager (9 K). Details of the design methods used to achieve the spectral requirements, selection of thin film materials, deposition technique, and testing are presented together with the optical layout of the instrument. (C) 2008 Optical Society of America.

Multiple-scattering in radar systems: a review

Although extensively studied within the lidar community, the multiple scattering phenomenon has always been considered a rare curiosity by radar meteorologists. Up to few years ago its appearance has only been associated with two- or three-body-scattering features (e.g. hail flares and mirror images) involving highly reflective surfaces. Recent atmospheric research aimed at better understanding of the water cycle and the role played by clouds and precipitation in affecting the Earth's climate has driven the deployment of high frequency radars in space. Examples are the TRMM 13.5 GHz, the CloudSat 94 GHz, the upcoming EarthCARE 94 GHz, and the GPM dual 13-35 GHz radars. These systems are able to detect the vertical distribution of hydrometeors and thus provide crucial feedbacks for radiation and climate studies. The shift towards higher frequencies increases the sensitivity to hydrometeors, improves the spatial resolution and reduces the size and weight of the radar systems. On the other hand, higher frequency radars are affected by stronger extinction, especially in the presence of large precipitating particles (e.g. raindrops or hail particles), which may eventually drive the signal below the minimum detection threshold. In such circumstances the interpretation of the radar equation via the single scattering approximation may be problematic. Errors will be large when the radiation emitted from the radar after interacting more than once with the medium still contributes substantially to the received power. This is the case if the transport mean-free-path becomes comparable with the instrument footprint (determined by the antenna beam-width and the platform altitude). This situation resembles to what has already been experienced in lidar observations, but with a predominance of wide- versus small-angle scattering events. At millimeter wavelengths, hydrometeors diffuse radiation rather isotropically compared to the visible or near infrared region where scattering is predominantly in the forward direction. A complete understanding of radiation transport modeling and data analysis methods under wide-angle multiple scattering conditions is mandatory for a correct interpretation of echoes observed by space-borne millimeter radars. This paper reviews the status of research in this field. Different numerical techniques currently implemented to account for higher order scattering are reviewed and their weaknesses and strengths highlighted. Examples of simulated radar backscattering profiles are provided with particular emphasis given to situations in which the multiple scattering contributions become comparable or overwhelm the single scattering signal. We show evidences of multiple scattering effects from air-borne and from CloudSat observations, i.e. unique signatures which cannot be explained by single scattering theory. Ideas how to identify and tackle the multiple scattering effects are discussed. Finally perspectives and suggestions for future work are outlined. This work represents a reference-guide for studies focused at modeling the radiation transport and at interpreting data from high frequency space-borne radar systems that probe highly opaque scattering media such as thick ice clouds or precipitating clouds.

Spectrally-invariant behavior of zenith radiance around cloud edges simulated by radiative transfer

In a previous paper, we discovered a surprising spectrally-invariant relationship in shortwave spectrometer observations taken by the Atmospheric Radiation Measurement (ARM) program. The relationship suggests that the shortwave spectrum near cloud edges can be determined by a linear combination of zenith radiance spectra of the cloudy and clear regions. Here, using radiative transfer simulations, we study the sensitivity of this relationship to the properties of aerosols and clouds, to the underlying surface type, and to the finite field-of-view (FOV) of the spectrometer. Overall, the relationship is mostly sensitive to cloud properties and has little sensitivity to other factors. At visible wavelengths, the relationship primarily depends on cloud optical depth regardless of cloud phase function, thermodynamic phase and drop size. At water-absorbing wavelengths, the slope of the relationship depends primarily on cloud optical depth; the intercept, by contrast, depends primarily on cloud absorbing and scattering properties, suggesting a new retrieval method for cloud drop effective radius. These results suggest that the spectrally-invariant relationship can be used to infer cloud properties near cloud edges even with insufficient or no knowledge about spectral surface albedo and aerosol properties.

Spectral invariant behavior of zenith radiance around cloud edges observed by ARM SWS

The ARM Shortwave Spectrometer (SWS) measures zenith radiance at 418 wavelengths between 350 and 2170 nm. Because of its 1-sec sampling resolution, the SWS provides a unique capability to study the transition zone between cloudy and clear sky areas. A spectral invariant behavior is found between ratios of zenith radiance spectra during the transition from cloudy to cloud-free. This behavior suggests that the spectral signature of the transition zone is a linear mixture between the two extremes (definitely cloudy and definitely clear). The weighting function of the linear mixture is a wavelength-independent characteristic of the transition zone. It is shown that the transition zone spectrum is fully determined by this function and zenith radiance spectra of clear and cloudy regions. An important result of these discoveries is that high temporal resolution radiance measurements in the clear-to-cloud transition zone can be well approximated by lower temporal resolution measurements plus linear interpolation.

Remote sensing of cloud properties using ground-based measurements of zenith radiance

We have conducted the first extensive field test of two new methods to retrieve optical properties for overhead clouds that range from patchy to overcast. The methods use measurements of zenith radiance at 673 and 870 nm wavelengths and require the presence of green vegetation in the surrounding area. The test was conducted at the Atmospheric Radiation Measurement Program Oklahoma site during September–November 2004. These methods work because at 673 nm (red) and 870 nm (near infrared (NIR)), clouds have nearly identical optical properties, while vegetated surfaces reflect quite differently. The first method, dubbed REDvsNIR, retrieves not only cloud optical depth τ but also radiative cloud fraction. Because of the 1-s time resolution of our radiance measurements, we are able for the first time to capture changes in cloud optical properties at the natural timescale of cloud evolution. We compared values of τ retrieved by REDvsNIR to those retrieved from downward shortwave fluxes and from microwave brightness temperatures. The flux method generally underestimates τ relative to the REDvsNIR method. Even for overcast but inhomogeneous clouds, differences between REDvsNIR and the flux method can be as large as 50%. In addition, REDvsNIR agreed to better than 15% with the microwave method for both overcast and broken clouds. The second method, dubbed COUPLED, retrieves τ by combining zenith radiances with fluxes. While extra information from fluxes was expected to improve retrievals, this is not always the case. In general, however, the COUPLED and REDvsNIR methods retrieve τ to within 15% of each other.

Improvements in or relating to the manufacture of multilayer interference filters

This invention relates to the manufacture of multi-layer interference filters for use with infra-red radiation, especially at wavelengths beyond 3.8 microns. A method of manufacturing a multi-layer interference filter comprising the steps of forming on a substrate successive layers of lead telluride and another material in alternation, under conditions in which sufficient oxygen is included in the lead telluride layers to reduce the apparent free charge carrier concentration therein, so that the resulting filter exhibits enhanced transparency to radiation of wavelengths greater than 3.8 microns and enhanced natural absorption to radiation of wavelength less than 3.8 microns.

Measurement of infrared multilayer filters at temperatures down to 4 deg K

Measurement is reported at 4 deg K (and blocked transmission below 10-5) of PbTe/ZnS thin-film filters deposited on Ge substrates. The reduced carrier-absorption which is obtained by cooling these PbTe films is found to accord with simple theory. Advantage for various high-performance multilayers by cooling is significant at the longer wavelengths, and has been verified.

Far infrared filters for the GALILEO-Jupiter and other missions

Extrapolation of PbTe/II-VI multilayer interference-filter technique from 20 to beyond 40µm is described and PbTe transparency reviewed; improvements below 20µm are reported. A composite filter cutting on steeply at 40µm is described that uses absorptive films of ZnS and As2S3, thin Quartz, and supplementary multilayer interference. Absorptive filters are described containing the II-VI compounds since these are found transparent at wavelengths shorter and longer than their reststrahl.

Do in vivo terahertz imaging systems comply with safety guidelines?

Techniques for the coherent generation and detection of electromagnetic radiation in the far infrared, or terahertz, region of the electromagnetic spectrum have recently developed rapidly and may soon be applied for in vivo medical imaging. Both continuous wave and pulsed imaging systems are under development, with terahertz pulsed imaging being the more common method. Typically a pump and probe technique is used, with picosecond pulses of terahertz radiation generated from femtosecond infrared laser pulses, using an antenna or nonlinear crystal. After interaction with the subject either by transmission or reflection, coherent detection is achieved when the terahertz beam is combined with the probe laser beam. Raster scanning of the subject leads to an image data set comprising a time series representing the pulse at each pixel. A set of parametric images may be calculated, mapping the values of various parameters calculated from the shape of the pulses. A safety analysis has been performed, based on current guidelines for skin exposure to radiation of wavelengths 2.6 µm–20 mm (15 GHz–115 THz), to determine the maximum permissible exposure (MPE) for such a terahertz imaging system. The international guidelines for this range of wavelengths are drawn from two U.S. standards documents. The method for this analysis was taken from the American National Standard for the Safe Use of Lasers (ANSI Z136.1), and to ensure a conservative analysis, parameters were drawn from both this standard and from the IEEE Standard for Safety Levels with Respect to Human Exposure to Radio Frequency Electromagnetic Fields (C95.1). The calculated maximum permissible average beam power was 3 mW, indicating that typical terahertz imaging systems are safe according to the current guidelines. Further developments may however result in systems that will exceed the calculated limit. Furthermore, the published MPEs for pulsed exposures are based on measurements at shorter wavelengths and with pulses of longer duration than those used in terahertz pulsed imaging systems, so the results should be treated with caution.

An introduction to medical imaging with coherent terahertz frequency radiation

Methods have recently been developed that make use of electromagnetic radiation at terahertz (THz) frequencies, the region of the spectrum between millimetre wavelengths and the infrared, for imaging purposes. Radiation at these wavelengths is non-ionizing and subject to far less Rayleigh scatter than visible or infrared wavelengths, making it suitable for medical applications. This paper introduces THz pulsed imaging and discusses its potential for in vivo medical applications in comparison with existing modalities.

A new micro-machined millimeter-wave and terahertz snap-together rectangular waveguide technology

A novel technique for micro-machining millimeter and submillimeter-wave rectangular waveguide components is reported. These are fabricated in two halves which simply snap together, utilizing locating pins and holes, and are physically robust, and cheap, and easy to manufacture. In addition, S-parameter measurements on these structures are reported for the first time and display lower loss than previously reported micro-machined rectangular waveguides.

Was UV spectral solar irradiance lower during the recent low sunspot minimum?

A detailed analysis is presented of solar UV spectral irradiance for the period between May 2003 and August 2005, when data are available from both the Solar Ultraviolet pectral Irradiance Monitor (SUSIM) instrument (on board the pper Atmosphere Research Satellite (UARS) spacecraft) and the Solar Stellar Irradiance Comparison Experiment (SOLSTICE) instrument (on board the Solar Radiation and Climate Experiment (SORCE) satellite). The ultimate aim is to develop a data composite that can be used to accurately determine any differences between the “exceptional” solar minimum at the end of solar cycle 23 and the previous minimum at the end of solar cycle 22 without having to rely on proxy data to set the long‐term change. SUSIM data are studied because they are the only data available in the “SOLSTICE gap” between the end of available UARS SOLSTICE data and the start of the SORCE data. At any one wavelength the two data sets are considered too dissimilar to be combined into a meaningful composite if any one of three correlations does not exceed a threshold of 0.8. This criterion removes all wavelengths except those in a small range between 156 nm and 208 nm, the longer wavelengths of which influence ozone production and heating in the lower stratosphere. Eight different methods are employed to intercalibrate the two data sequences. All methods give smaller changes between the minima than are seen when the data are not adjusted; however, correcting the SUSIM data to allow for an exponentially decaying offset drift gives a composite that is largely consistent with the unadjusted data from the SOLSTICE instruments on both UARS and SORCE and in which the recent minimum is consistently lower in the wave band studied.

Determination by MAD-DM of the structure of the DNA duplex d[ACGTACG(5-BrU)]2 at 1.46 Å and 100 K

A four-wavelength MAD experiment on a new brominated octanucleotide is reported here. d[ACGTACG(5-BrU)], C77H81BrN30O32P7, (DNA) = 2235, tetragonal, P43212 (No. 96), a = 43.597, c = 26.268 Å, V = 49927.5 Å3, Z = 8, T = 100 K, R = 10.91% for 4312 reflections between 15.0 and 1.46 Å resolution. The self-complementary brominated octanucleotide d[ACGTACG(5-BrU)]2 has been crystallized and data measured to 1.45 Å at both 293 K and a second crystal flash frozen at 100 K. The latter data collection was carried out to the same resolution at the four wavelengths 0.9344, 0.9216, 0.9208 and 0.9003 Å, around the Br K edge at 0.92 Å and the structure determined from a map derived from a MAD data analysis using pseudo-MIR methodology, as implemented in the program MLPHARE. This is one of the first successful MAD phasing experiments carried out at Sincrotrone Elettra in Trieste, Italy. The structure was refined using the data measured at 0.9003 Å, anisotropic temperature factors and the restrained least-squares refinement implemented in the program SHELX96, and the helical parameters are compared with those previously determined for the isomorphous d(ACGTACGT)2 analogue. The asymmetric unit consists of a single strand of octamer with 96 water molecules. No countercations were located. The A-DNA helix geometry obtained has been analysed using the CURVES program.