673 research outputs found
Surveying the Precautionary Principle\u27s Ongoing Global Development: The Evolution of an Emergent Environmental Management Tool
The precautionary principle, which many trace back to German regulations promulgated in the early 1970s, has developed into an important environmental management tool. Its inclusion in numerous international treaties and agreements over the past seventeen years confirms its significance. Beyond international treaties, many foreign governments have explored the application of the precautionary principle to their own decisionmaking procedures. For instance, the precautionary principle has been the central focus of judicial decisions in Australia, Canada, and India. Despite this growing global acceptance and implementation of the precautionary principle, the United States has remained adamantly opposed to its introduction into domestic policy. This Note focuses on international application or non-application of the precautionary principle in order to better understand the United States’ current opposition. Ultimately, this comparative analysis should clarify, which, if any, governmental avenue will prove most effective in laying the foundation for implementation of the precautionary principle in this country
Isomerization Mechanism in Hydrazone-Based Rotary Switches: Lateral Shift, Rotation, or Tautomerization?
Two intramolecularly hydrogen-bonded arylhydrazone (aryl = phenyl or naphthyl) molecular switches have been synthesized, and their full and reversible switching between the E and Z configurations have been demonstrated. These chemically controlled configurational rotary switches exist primarily as the E isomer at equilibrium and can be switched to the protonated Z configuration (Z-H^+) by the addition of trifluoroacetic acid. The protonation of the pyridine moiety in the switch induces a rotation around the hydrazone C═N double bond, leading to isomerization. Treating Z-H^+ with base (K_(2)CO_3) yields a mixture of E and “metastable” Z isomers. The latter thermally equilibrates to reinstate the initial isomer ratio. The rate of the Z → E isomerization process showed small changes as a function of solvent polarity, indicating that the isomerization might be going through the inversion mechanism (nonpolar transition state). However, the plot of the logarithm of the rate constant k vs the Dimroth parameter (E_T) gave a linear fit, demonstrating the involvement of a polar transition state (rotation mechanism). These two seemingly contradicting kinetic data were not enough to determine whether the isomerization mechanism goes through the rotation or inversion pathways. The highly negative entropy values obtained for both the forward (E → Z-H^+) and backward (Z → E) processes strongly suggest that the isomerization involves a polarized transition state that is highly organized (possibly involving a high degree of solvent organization), and hence it proceeds via a rotation mechanism as opposed to inversion. Computations of the Z ↔ E isomerization using density functional theory (DFT) at the M06/cc-pVTZ level and natural bond orbital (NBO) wave function analyses have shown that the favorable isomerization mechanism in these hydrogen-bonded systems is hydrazone–azo tautomerization followed by rotation around a C–N single bond, as opposed to the more common rotation mechanism around the C═N double bond
Thyrotoxicosis in a 13-year-old girl following pituitary adenectomy for Cushing's disease.
To access publisher's full text version of this article, please click on the hyperlink in Additional Links field or click on the hyperlink at the top of the page marked FilesOur objective is to report a case of thyrotoxicosis following pituitary adenectomy for Cushing's disease, the only pediatric case to our knowledge. No thyroid antibodies were detected, and the thyrotoxicosis was successfully treated for 3 months with no relapse after 5 years of follow-up. The cause of thyrotoxicosis remains unknown
Measurement of atmospheric nitrous acid at Blodgett Forest during BEARPEX2007
Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) in the lower troposphere. Understanding HONO chemistry, particularly its sources and contribution to HO_x (=OH+HO_2) production, is very important for understanding atmospheric oxidation processes. A highly sensitive instrument for detecting atmospheric HONO based on wet chemistry followed by liquid waveguide long path absorption photometry was deployed in the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at Blodgett Forest, California in late summer 2007. The median diurnal variation shows minimum HONO levels of about 20–30 pptv during the day and maximum levels of about 60–70 pptv at night, a diurnal pattern quite different from the results at various other forested sites. Measured HONO/NO_2 ratios for a 24-h period ranged from 0.05 to 0.13 with a mean ratio of 0.07. Speciation of reactive nitrogen compounds (NO_y) indicates that HONO accounted for only ~3% of total NO_y. However, due to the fast HONO loss through photolysis, a strong HONO source (1.59 ppbv day^(−1)) existed in this environment in order to sustain the observed HONO levels, indicating the significant role of HONO in NO_y cycling. The wet chemistry HONO measurements were compared to the HONO measurements made with a Chemical Ionization Mass Spectrometer (CIMS) over a three-day period. Good agreement was obtained between the measurements from the two different techniques. Using the expansive suite of photochemical and meteorological measurements, the contribution of HONO photolysis to HO_x budget was calculated to be relatively small (6%) compared to results from other forested sites. The lower HONO mixing ratio and thus its smaller contribution to HO_x production are attributed to the unique meteorological conditions and low acid precipitation at Blodgett Forest. Further studies of HONO in this kind of environment are needed to test this hypothesis and to improve our understanding of atmospheric oxidation and nitrogen budget
Atmospheric benzene observations from oil and gas production in the Denver-Julesburg Basin in July and August 2014
High time resolution measurements of volatile organic compounds (VOCs) were collected using a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the Platteville Atmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (O&NG) development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA’s “Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality” (DISCOVER-AQ) field campaign. The PTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO
Measurement of atmospheric nitrous acid at Bodgett Forest during BEARPEX2007
Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) in the lower troposphere. Understanding HONO chemistry, particularly its sources and contribution to HO<sub>x</sub> (=OH+HO<sub>2</sub>) production, is very important for understanding atmospheric oxidation processes. A highly sensitive instrument for detecting atmospheric HONO based on wet chemistry followed by liquid waveguide long path absorption photometry was deployed in the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at Blodgett Forest, California in late summer 2007. The median diurnal variation shows minimum HONO levels of about 20–30 pptv during the day and maximum levels of about 60–70 pptv at night, a diurnal pattern quite different from the results at various other forested sites. Measured HONO/NO<sub>2</sub> ratios for a 24-h period ranged from 0.05 to 0.13 with a mean ratio of 0.07. Speciation of reactive nitrogen compounds (NO<sub>y</sub>) indicates that HONO accounted for only ~3% of total NO<sub>y</sub>. However, due to the fast HONO loss through photolysis, a strong HONO source (1.59 ppbv day<sup>−1</sup>) existed in this environment in order to sustain the observed HONO levels, indicating the significant role of HONO in NO<sub>y</sub> cycling. The wet chemistry HONO measurements were compared to the HONO measurements made with a Chemical Ionization Mass Spectrometer (CIMS) over a three-day period. Good agreement was obtained between the measurements from the two different techniques. Using the expansive suite of photochemical and meteorological measurements, the contribution of HONO photolysis to HO<sub>x</sub> budget was calculated to be relatively small (6%) compared to results from other forested sites. The lower HONO mixing ratio and thus its smaller contribution to HO<sub>x</sub> production are attributed to the unique meteorological conditions and low acid precipitation at Blodgett Forest. Further studies of HONO in this kind of environment are needed to test this hypothesis and to improve our understanding of atmospheric oxidation and nitrogen budget
Assessing fossil fuel CO_2 emissions in California using atmospheric observations and models
Analysis systems incorporating atmospheric observations could provide a powerful tool for validating fossil fuel CO_2 (ffCO_2) emissions reported for individual regions, provided that fossil fuel sources can be separated from other CO_2 sources or sinks and atmospheric transport can be accurately accounted for. We quantified ffCO_2 by measuring radiocarbon (^(14)C) in CO_2, an accurate fossil-carbon tracer, at nine observation sites in California for three months in 2014–15. There is strong agreement between the measurements and ffCO_2 simulated using a high-resolution atmospheric model and a spatiotemporally-resolved fossil fuel flux estimate. Inverse estimates of total in-state ffCO_2 emissions are consistent with the California Air Resources Board's reported ffCO_2 emissions, providing tentative validation of California's reported ffCO_2 emissions in 2014–15. Continuing this prototype analysis system could provide critical independent evaluation of reported ffCO_2 emissions and emissions reductions in California, and the system could be expanded to other, more data-poor regions
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CFD Model Analysis and Validation for a Formula SAE Racecar
This project examines the computational fluid dynamics (CFD) model used by Global Formula Racing (GFR) to simulate external aerodynamics for a Formula SAE racecar. It seeks to improve the accuracy of the existing model by changing mesh and physics model parameters. Accuracy of the model is quantified through comparison to physical experimental data. Mesh parameters studied include prism layer properties, wake refinement, and volumetric control use. Multiple turbulence models are compared, and sensitivity to initial conditions and boundary conditions is quantified. A recommended half-car mesh and physics model is produced, and recommendations for further development are added
A genome-wide screening uncovers the role of CCAR2 as an antagonist of DNA end resection
There are two major and alternative pathways to repair DNA double-strand breaks: non-homologous end-joining and homologous recombination. Here we identify and characterize novel factors involved in choosing between these pathways; in this study we took advantage of the SeeSaw Reporter, in which the repair of double-strand breaks by homology-independent or -dependent mechanisms is distinguished by the accumulation of green or red fluorescence, respectively. Using a genome-wide human esiRNA (endoribonuclease- prepared siRNA) library, we isolate genes that control the recombination/endjoining ratio. Here we report that two distinct sets of genes are involved in the control of the balance between NHEJ and HR: those that are required to facilitate recombination and those that favour NHEJ. This last category includes CCAR2/DBC1, which we show inhibits recombination by limiting the initiation and the extent of DNA end resection, thereby acting as an antagonist of CtIP
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