Biomass Derived, Hierarchically Porous, Activated Starbons® as Adsorbents for Volatile Organic Compounds.

The use of potassium hydroxide activated Starbons® derived from starch and alginic acid as adsorbents for 29 volatile organic compounds (VOCs) was investigated. In every case, the alginic acid derived Starbon (A800K2) was found to be the optimal adsorbent, significantly outperforming both commercial activated carbon and starch derived, activated Starbon (S800K2). The saturated adsorption capacity of A800K2 depends on both the size of the VOC and the functional groups it contains. The highest saturated adsorption capacities were obtained with small VOCs. For VOC's of similar size, the presence of polarizable electrons in lone pairs or π-bonds within non-polar VOCs was beneficial. Analysis of porosimetry data suggests that the VOC's are being adsorbed within the pore structure of A800K2 rather than just on its surface. The adsorption was completely reversible by thermal treatment of the saturated Starbon under vacuum.

Dichloromethane replacement: towards greener chromatography via Kirkwood-Buff integrals.

Dichloromethane (DCM) is a useful and advantageous solvent used in pharmaceutical development due to its low cost, miscibility with other organic solvents, high volatility, and ability to solubilize drug molecules of variable polarities and functionalities. Despite this favourable behaviour, efforts to identify safer and more sustainable alternatives to hazardous, halogenated solvents is imperative to the expansion of green chemistry. In this work, bio-derived esters tert-butyl acetate, sec-butyl acetate, ethyl isobutyrate, and methyl pivalate are experimentally identified as safe and sustainable alternatives to directly replace DCM within thin-layer chromatography (TLC) in the analysis of small, common drug molecules. To elucidate the intermolecular interactions influencing retardation factors (Rf) a statistical thermodynamic framework, which quantifies the driving molecular interactions that yield empirical TLC measurements, is presented. Within this framework, we are able to deduce Rf dependence on polar eluent concentration, in the presence of a low-polar mediating solvent, between the stationary and mobile phases. The strength of competitive analyte-eluent (and analyte-solvent interactions) are quantified through Kirkwood-Buff integrals (KBIs); resulting KBI terms at the dilute eluent limit provide a theoretical foundation for the observed suitability of alternative green solvents for the replacement of dichloromethane in TLC.

Industry-Informed Workshops to Develop Graduate Skill Sets in the Circular Economy Using Systems Thinking.

Increasing demand for chemicals worldwide, depleting resources, consumer pressure, stricter legislation, and the rising cost of waste disposal are placing increasing pressure on chemical and related industries. For any organization to survive in the current arena of growing climate change laws and regulations, and increasing public influence, the issue of sustainability must be fundamental to the way it operates. A sustainable manufacturing approach will enable economic growth to be combined with environmental and social sustainability and will be realized via collaboration between a multidisciplinary community including chemists, biologists, engineers, environmental scientists, economists, experts in management, and policy makers. Hence, employees with new skills, knowledge, and experience are essential. To realize this approach, the design and development of a series of workshops encompassing systems thinking are presented here. After close consultation with industry, an annual program of interactive workshops has been designed for graduate students to go beyond examining the "greening" of chemical reactions, processes, and products, and instead embed a systems thinking approach to learning. The workshops provide a valuable insight into the issues surrounding sustainable manufacturing covering change management, commercialization, environmental impact, circular economy, legislation, and bioresources incorporating the conversion of waste into valuable products. The multidisciplinary course content incorporates industrial case studies, providing access to real business issues, and is delivered by experts from academic departments across campus and industry.

Tropospheric Emissions: Monitoring of Pollution (TEMPO).

TEMPO was selected in 2012 by NASA as the first Earth Venture Instrument, for launch between 2018 and 2021. It will measure atmospheric pollution for greater North America from space using ultraviolet and visible spectroscopy. TEMPO observes from Mexico City, Cuba, and the Bahamas to the Canadian oil sands, and from the Atlantic to the Pacific, hourly and at high spatial resolution (~2.1 km N/S×4.4 km E/W at 36.5°N, 100°W). TEMPO provides a tropospheric measurement suite that includes the key elements of tropospheric air pollution chemistry, as well as contributing to carbon cycle knowledge. Measurements are made hourly from geostationary (GEO) orbit, to capture the high variability present in the diurnal cycle of emissions and chemistry that are unobservable from current low-Earth orbit (LEO) satellites that measure once per day. The small product spatial footprint resolves pollution sources at sub-urban scale. Together, this temporal and spatial resolution improves emission inventories, monitors population exposure, and enables effective emission-control strategies. TEMPO takes advantage of a commercial GEO host spacecraft to provide a modest cost mission that measures the spectra required to retrieve ozone (O3), nitrogen dioxide (NO2), sulfur dioxide (SO2), formaldehyde (H2CO), glyoxal (C2H2O2), bromine monoxide (BrO), IO (iodine monoxide),water vapor, aerosols, cloud parameters, ultraviolet radiation, and foliage properties. TEMPO thus measures the major elements, directly or by proxy, in the tropospheric O3 chemistry cycle. Multi-spectral observations provide sensitivity to O3 in the lowermost troposphere, substantially reducing uncertainty in air quality predictions. TEMPO quantifies and tracks the evolution of aerosol loading. It provides these near-real-time air quality products that will be made publicly available. TEMPO will launch at a prime time to be the North American component of the global geostationary constellation of pollution monitoring together with the European Sentinel-4 (S4) and Korean Geostationary Environment Monitoring Spectrometer (GEMS) instruments.

Ground-based assessment of the bias and long-term stability of fourteen limb and occultation ozone profile data records.

The ozone profile records of a large number of limb and occultation satellite instruments are widely used to address several key questions in ozone research. Further progress in some domains depends on a more detailed understanding of these data sets, especially of their long-term stability and their mutual consistency. To this end, we made a systematic assessment of fourteen limb and occultation sounders that, together, provide more than three decades of global ozone profile measurements. In particular, we considered the latest operational Level-2 records by SAGE II, SAGE III, HALOE, UARS MLS, Aura MLS, POAM II, POAM III, OSIRIS, SMR, GOMOS, MIPAS, SCIAMACHY, ACE-FTS and MAESTRO. Central to our work is a consistent and robust analysis of the comparisons against the ground-based ozonesonde and stratospheric ozone lidar networks. It allowed us to investigate, from the troposphere up to the stratopause, the following main aspects of satellite data quality: long-term stability, overall bias, and short-term variability, together with their dependence on geophysical parameters and profile representation. In addition, it permitted us to quantify the overall consistency between the ozone profilers. Generally, we found that between 20-40 km the satellite ozone measurement biases are smaller than ±5 %, the short-term variabilities are less than 5-12% and the drifts are at most ±5% decade-1 (or even ±3 % decade-1 for a few records). The agreement with ground-based data degrades somewhat towards the stratopause and especially towards the tropopause where natural variability and low ozone abundances impede a more precise analysis. In part of the stratosphere a few records deviate from the preceding general conclusions; we identified biases of 10% and more (POAM II and SCIAMACHY), markedly higher single-profile variability (SMR and SCIAMACHY), and significant long-term drifts (SCIAMACHY, OSIRIS, HALOE, and possibly GOMOS and SMR as well). Furthermore, we reflected on the repercussions of our findings for the construction, analysis and interpretation of merged data records. Most notably, the discrepancies between several recent ozone profile trend assessments can be mostly explained by instrumental drift. This clearly demonstrates the need for systematic comprehensive multi-instrument comparison analyses.

Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents.

Dihydrolevoglucosenone (Cyrene) is a bio-based molecule, derived in two simple steps from cellulose, which demonstrates significant promise as a dipolar aprotic solvent. The dipolarity of dihydrolevoglucosenone is similar to NMP, DMF and sulpholane. Dihydrolevoglucosenone demonstrates similar performance to NMP in a fluorination reaction and the Menschutkin reaction.

New technique for retrieval of atmospheric temperature profiles from Rayleigh-scatter lidar measurements using nonlinear inversion.

The conventional method of calculating atmospheric temperature profiles using Rayleigh-scattering lidar measurements has limitations that necessitate abandoning temperatures retrieved at the greatest heights, due to the assumption of a pressure value required to initialize the integration at the highest altitude. An inversion approach is used to develop an alternative way of retrieving nightly atmospheric temperature profiles from the lidar measurements. Measurements obtained by the Purple Crow lidar facility located near The University of Western Ontario are used to develop and test this new technique. Our results show temperatures can be reliably retrieved at all heights where measurements with adequate signal-to-noise ratio exist. A Monte Carlo technique was developed to provide accurate estimates of both the systematic and random uncertainties for the retrieved nightly average temperature profile. An advantage of this new method is the ability to seed the temperature integration from the lowest rather than the greatest height, where the variability of the pressure is smaller than in the mesosphere or lower thermosphere and may in practice be routinely measured by a radiosonde, rather than requiring a rocket or satellite-borne measurement. Thus, this new technique extends the altitude range of existing Rayleigh-scatter lidars 10-15 km, producing the equivalent of four times the power-aperture product.

Unprecedented Arctic ozone loss in 2011.

Chemical ozone destruction occurs over both polar regions in local winter-spring. In the Antarctic, essentially complete removal of lower-stratospheric ozone currently results in an ozone hole every year, whereas in the Arctic, ozone loss is highly variable and has until now been much more limited. Here we demonstrate that chemical ozone destruction over the Arctic in early 2011 was--for the first time in the observational record--comparable to that in the Antarctic ozone hole. Unusually long-lasting cold conditions in the Arctic lower stratosphere led to persistent enhancement in ozone-destroying forms of chlorine and to unprecedented ozone loss, which exceeded 80 per cent over 18-20 kilometres altitude. Our results show that Arctic ozone holes are possible even with temperatures much milder than those in the Antarctic. We cannot at present predict when such severe Arctic ozone depletion may be matched or exceeded.

Correlated electron state in Ce(1-x)Yb(x)CoIn5 stabilized by cooperative valence fluctuations.

X-ray diffraction, electrical resistivity, magnetic susceptibility, and specific heat measurements on Ce(1-x)Yb(x)CoIn5 (0≤x≤1) reveal that many of the characteristic features of the x=0 correlated electron state are stable for x≤0.775 and that phase separation occurs for x>0.775. The stability of the correlated electron state is apparently due to cooperative behavior of the Ce and Yb ions, involving their unstable valences. Low-temperature non-Fermi liquid behavior is observed and varies with x, even though there is no readily identifiable quantum critical point. The superconducting critical temperature T(c) decreases linearly with x towards 0 K as x→1, in contrast with other HF superconductors where T(c) scales with T(coh).

The ACE-MAESTRO instrument on SCISAT: description, performance, and preliminary results.

The Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (MAESTRO) instrument on the SCISAT satellite is a simple, compact spectrophotometer for the measurement of atmospheric extinction, ozone, nitrogen dioxide, and other trace gases in the stratosphere and upper troposphere as part of the Atmospheric Chemistry Experiment (ACE) mission. We provide an overview of the instrument from requirements to realization, including optical design, prelaunch and on-orbit performance, and a preliminary examination of retrievals of ozone and NO(2).

Simultaneous measurements of visible (400-700 nm) and infrared (3.4 microm) NO(2) absorption.

Laboratory measurements of NO(2) absorption were obtained in the visible (400-700 nm) and mid-infrared (3.4 mum) regions simultaneously using SCISAT-1's ACE-FTS (atmospheric chemistry experiment-Fourier transform spectrometer) and MAESTRO (measurement of aerosol extinction in the stratosphere and troposphere retrieved by occultation) spectrometers. An intercomparison of these measurements was used to verify the consistency between the HITRAN 2004 3.4-mum band strengths and the strengths of three different visible cross section data sets. These measurements should be of interest to the remote-sensing community, since NO(2) measurements obtained by infrared-range instruments are often compared to those obtained by visible-range instruments without accurate knowledge of the consistency between the visible and infrared absorption coefficients. Two significant results were obtained in this study: (1) A 0.5% agreement was found between the HITRAN 2004 line strengths and the Vandaele et al. (Vandaele, A. C.; Hermans, C.; Fally, S.; Carleer, M.; Colin, R.; Mérienne, M.-F.; Jenouvrier, A.; Coquart, B. J. Geophys. Res. 2002, 107 (D18), 4348) temperature-corrected cross sections, and (2) the mean pressure-broadened half-width of NO(2) by NO in the 3.4-mum band was measured as being 0.096 +/- 0.001 cm(-1) atm(-1). The latter finding is thought to be unreported by the literature.

Intercomparison of simultaneously obtained infrared (4.8 microm) and visible (515-715 nm) ozone spectra using ACE-FTS and MAESTRO.

Laboratory ozone absorption spectra were measured simultaneously in the visible (515-715 nm) and infrared (2070-2140 cm(-1)) spectral regions using SCISAT-1's MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and ACE-FTS (Atmospheric Chemistry Experiment-Fourier Transform Spectrometer) spectrometers. An intercomparison of these measurements was used to assess the relative accuracy of HITRAN absolute line strengths, for which there was a 4% change between the 2000 and 2004 versions. Results reported here show that Chappuis band cross section strengths are more consistent with the HITRAN 2004 4.8 microm band line strengths than with the 2000 compilation.

Long-wavelength polarizing cutoff filters for the 275-550-nm spectral region.

The design and manufacture of a multiple-reflection-type multilayer element is described that efficiently removes all wavelengths higher than 550 nm from the incident radiation and that at the same time acts as a polarizer in the 275-550-nm spectral transmission region.

Black layer coatings for the photolithographic manufacture of diffraction gratings.

A black layer coating for an aluminum-photoresist interface with a reflectance less than 0.1% for 413-nm, s-polarized light incident at 25 degrees is described. It is made of space-compatible materials, and its rms roughness is less than 15 A.

The team approach in the management of congenital and acquired deformities.

This article provides a summary of practices and guidelines for the design and methods used to form interdisciplinary medical teams. Education and organizational resources are discussed with regard to children with congenital anomalies, specifically craniofacial and cleft lip and palate deformities. The team format is recommended to maximize efficiencies and assure a continuum of care in the evolving managed care environment.

Investigation of the wavelength accuracy of brewer spectrophotometers.

The wavelength accuracy of the Brewer spectrophotometer in the 280-360-nm spectral range is improved by a new grating-drive mechanism and a new dispersion function derived from the Brewer geometry. With the new mechanism, the reproducibility of wavelength settings for spectral emission lines is better than 0.3 pm (0.0003 nm) and, with a thermally compensated version, the effect of temperature is less than 0.4 pm K(-1). The new dispersion function fits spectral line positions better than the standard function and is less prone to extrapolation error. Applying the new function to data from four new and ten standard drives shows that the new drives perform as well as the best of the standard ones and much better than the majority.

Neonatal rotavirus infection in Bangladesh: strain characterization and risk factors for nosocomial infection.

BACKGROUND: Rotavirus (RV) diarrhea is an important cause of childhood morbidity and mortality in Bangladesh and is responsible for 24% of hospital admissions for diarrhea in children from 3 months to 2 years of age. However, the prevalence of neonatal RV infections and characteristics of RV strains infecting neonates have not been explored in Bangladesh. METHODS: We investigated neonates at six hospitals in Bangladesh to determine the prevalence of neonatal RV infection, to identify risk factors for infection and to characterize neonatal RV strains by reverse transcription-polymerase chain reaction. RESULTS: Of 381 neonates screened at 6 hospitals 61 of 146 infants (42%) at 2 hospitals in Dhaka were RV-positive. Of these 62% were detected within the first 5 days of life. We found an increased risk for neonatal RV infection among infants whose mothers reported no handwashing during care of the neonate (P = 0.03). Analysis of RV strains in enzyme-linked immunosorbent assay-positive specimens identified P[6]G4 and P[6]G1 genotypes to be most common; 7% (2 of 27) of strains were nontypable. A concurrent analysis of RV strains circulating in Bangladesh suggested that RV genotypes infecting neonates had a distinct P genotype, because most community strains were P-nontypable compared with neonatal strains, which carried the P[6] genotype. CONCLUSIONS: Hospitalized neonates in Dhaka have increased risk for infection with RV as early as the first week of life with strains having the unusual P[6] genotype. Our findings confirm studies in India showing that neonatal RV infection can be common and may occur with strains distinct from those circulating in the community. Neonatal RV infections could alter a child's response to the RV vaccine as well as the calculation of RV vaccine efficacy in these populations.

Evidence for large upward trends of ultraviolet-B radiation linked to ozone depletion.

Spectral measurements of ultraviolet-B radiation made at Toronto since 1989 indicate that the intensity of light at wavelengths near 300 nanometers has increased by 35 percent per year in winter and 7 percent per year in summer. The wavelength dependence of these trends indicates that the increase is caused by the downward trend in total ozone that was measured at Toronto during the same period. The trend at wavelengths between 320 and 325 nanometers is essentially zero.

Lateral ventricular size and social network differentiation in young, nonchronic schizophrenic patients.

The authors correlated lateral cerebral ventricular size with social network differentiation and social outcome in 15 young, nonchronic patients with schizophrenia and schizophreniform disorder. Patients with fewer social contexts, fewer types of relationships, and less independent residence had larger ventricles.