In situ evidence for renitrification in the Arctic lower stratosphere during the polar aura validation experiment (PAVE)

In-situ measurements of nitric acid (HNO3), ozone (O3), and nitrous oxide (N2O) were made from the NASA DC-8 during the Polar Aura Validation Experiment in January/February 2005. In the lower stratosphere (9–12.5 km, potential temperature 300–350 K) characteristic compact relationships were observed between all three gases. The ratio HNO3/O3 averaged 3.5 (±0.7) ppt/ppb. Samples with enhanced HNO3/O3 (\u3e4.0) were most abundant under the edge of the Arctic Polar vortex in airmasses with enhanced mixing ratios of both gases (\u3e400 ppb O3 and \u3e2000 ppt HNO3) and reduced mixing ratios of N2O (\u3c305 ppb), indicating air from higher levels in the stratosphere. Relationships to N2O in the anomalous samples under the vortex edge indicate that increases in HNO3/O3 reflect renitrification at DC-8 flight levels, with no indication of significant O3 loss. Renitrified air was only observed at potential temperatures above 340 K, and was most abundant on the PAVE flights on 27 and 29 January

Modeling effects of L-type ca(2+) current and na(+)-ca(2+) exchanger on ca(2+) trigger flux in rabbit myocytes with realistic T-tubule geometries.

The transverse tubular system of rabbit ventricular myocytes consists of cell membrane invaginations (t-tubules) that are essential for efficient cardiac excitation-contraction coupling. In this study, we investigate how t-tubule micro-anatomy, L-type Ca(2+) channel (LCC) clustering, and allosteric activation of Na(+)/Ca(2+) exchanger by L-type Ca(2+) current affects intracellular Ca(2+) dynamics. Our model includes a realistic 3D geometry of a single t-tubule and its surrounding half-sarcomeres for rabbit ventricular myocytes. The effects of spatially distributed membrane ion-transporters (LCC, Na(+)/Ca(2+) exchanger, sarcolemmal Ca(2+) pump, and sarcolemmal Ca(2+) leak), and stationary and mobile Ca(2+) buffers (troponin C, ATP, calmodulin, and Fluo-3) are also considered. We used a coupled reaction-diffusion system to describe the spatio-temporal concentration profiles of free and buffered intracellular Ca(2+). We obtained parameters from voltage-clamp protocols of L-type Ca(2+) current and line-scan recordings of Ca(2+) concentration profiles in rabbit cells, in which the sarcoplasmic reticulum is disabled. Our model results agree with experimental measurements of global Ca(2+) transient in myocytes loaded with 50 μM Fluo-3. We found that local Ca(2+) concentrations within the cytosol and sub-sarcolemma, as well as the local trigger fluxes of Ca(2+) crossing the cell membrane, are sensitive to details of t-tubule micro-structure and membrane Ca(2+) flux distribution. The model additionally predicts that local Ca(2+) trigger fluxes are at least threefold to eightfold higher than the whole-cell Ca(2+) trigger flux. We found also that the activation of allosteric Ca(2+)-binding sites on the Na(+)/Ca(2+) exchanger could provide a mechanism for regulating global and local Ca(2+) trigger fluxes in vivo. Our studies indicate that improved structural and functional models could improve our understanding of the contributions of L-type and Na(+)/Ca(2+) exchanger fluxes to intracellular Ca(2+) dynamics

Puckering Free Energy of Pyranoses: an NMR and Metadynamics--Umbrella Sampling Investigation

We present the results of a combined metadynamics--umbrella sampling investigation of the puckered conformers of pyranoses described using the gromos 45a4 force field. The free energy landscape of Cremer--Pople puckering coordinates has been calculated for the whole series of alpha and beta aldohexoses, showing that the current force field parameters fail in reproducing proper puckering free energy differences between chair conformers. We suggest a modification to the gromos 45a4 parameter set which improves considerably the agreement of simulation results with theoretical and experimental estimates of puckering free energies. We also report on the experimental measurement of altrose conformers populations by means of NMR spectroscopy, which show good agreement with the predictions of current theoretical models

Impact of multiscale dynamical processes and mixing on the chemical composition of the upper troposphere and lower stratosphere during the Intercontinental Chemical Transport Experiment–North America

We use high-frequency in situ observations made from the DC8 to examine fine-scale tracer structure and correlations observed in the upper troposphere and lower stratosphere during INTEX-NA. Two flights of the NASA DC-8 are compared and contrasted. Chemical data from the DC-8 flight on 18 July show evidence for interleaving and mixing of polluted and stratospheric air masses in the vicinity of the subtropical jet in the upper troposphere, while on 2 August the DC-8 flew through a polluted upper troposphere and a lowermost stratosphere that showed evidence of an intrusion of polluted air. We compare data from both flights with RAQMS 3-D global meteorological and chemical model fields to establish dynamical context and to diagnose processes regulating the degree of mixing on each day. We also use trajectory mapping of the model fields to show that filamentary structure due to upstream strain deformation contributes to tracer variability observed in the upper troposphere. An Eulerian measure of strain versus rotation in the large-scale flow is found useful in predicting filamentary structure in the vicinity of the jet. Higher-frequency (6–24 km) tracer variability is attributed to buoyancy wave oscillations in the vicinity of the jet, whose turbulent dissipation leads to efficient mixing across tracer gradients

Constraints on the age and dilution of Pacific Exploratory Mission-Tropics biomass burning plumes from the natural radionuclide tracer 210Pb

During the NASA Global Troposphere Experiment Pacific Exploratory Mission-Tropics (PEM-Tropics) airborne sampling campaign we found unexpectedly high concentrations of aerosol-associated 210Pb throughout the free troposphere over the South Pacific. Because of the remoteness of the study region, we expected specific activities to be generally less than 35 μBq m−3 but found an average in the free troposphere of 107 μBq m−3. This average was elevated by a large number of very active (up to 405 μBq m−3) samples that were associated with biomass burning plumes encountered on nearly every PEM-Tropics flight in the southern hemisphere. We use a simple aging and dilution model, which assumes that 222Rn and primary combustion products are pumped into the free troposphere in wet convective systems over fire regions (most likely in Africa), to explain the elevated 210Pb activities. This model reproduces the observed 210Pb activities very well, and predicts the ratios of four hydrocarbon species (emitted by combustion) to CO to better than 20% in most cases. Plume ages calculated by the model depend strongly on the assumed 222Rn activities in the initial plume, but using values plausible for continental boundary layer air yields ages that are consistent with travel times from Africa to the South Pacific calculated with a back trajectory model. The model also shows that despite being easily recognized through the large enhancements of biomass burning tracers, these plumes must have entrained large fractions of the surrounding ambient air during transport

Anomalous scaling of mesoscale tropospheric humidity fluctuations

Water vapor fluctuations are measured and analyzed at an unprecedented 10-m resolution throughout the troposphere. Computation of structure functions shows that specific humidity variations observed by research aircraft over the Pacific Ocean exhibit anomalous scaling from about 50 m to 100 km in horizontal range. The scaling laws show different characteristics for the marine boundary layer, the tropical free troposphere, and the extratropical free troposphere. More specifically, boundary-layer humidity fluctuations are less smooth and more stationary than those in the free troposphere, while the extratropical free tropospheric variations are less intermittent than those in the other two regions. The anomalous scaling results argue against passive advection by a spatially smooth flow (chaotic advection) at these scales.United States. National Aeronautics and Space Administration (Grant NAG1-2173)United States. National Aeronautics and Space Administration (Grant NAG1-1901

Eastern Asian emissions of anthropogenic halocarbons deduced from aircraft concentration data

The Montreal Protocol restricts production of ozone-depleting halocarbons worldwide. Enforcement of the protocol has relied mainly on annual government statistics of production and consumption of these compounds (bottom-up approach). We show here that aircraft observations of halocarbon:CO enhancement ratios on regional to continental scales can be used to infer halocarbon emissions, providing independent verification of the bottom-up approach. We apply this top-down approach to aircraft observations of Asian outflow from the TRACE-P mission over the western Pacific (March April 2001) and derive emissions from eastern Asia (China, Japan, and Korea). We derive an eastern Asian carbon tetrachloride (CCl ) source of 21.5 Gg yr , several-fold larger than previous estimates and amounting to 30% of the global budget for this gas. Our emission estimate for CFC-11 from eastern Asia is 50% higher than inventories derived from manufacturing records. Our emission estimates for methyl chloroform (CH ) and CFC-12 are in agreement with existing inventories. For halon 1211 we find only a strong local source originating from the Shanghai area. Our emission estimates for the above gases result in a 40% increase in the ozone depletion potential (ODP) of Asian emissions relative to previous estimates, corresponding to a 10% global increase in ODP

In situ measurements of tropospheric volcanic plumes in Ecuador and Colombia during TC

A NASA DC‐8 research aircraft penetrated tropospheric gas and aerosol plumes sourced from active volcanoes in Ecuador and Colombia during the Tropical Composition, Cloud and Climate Coupling (TC4 ) mission in July–August 2007. The likely source volcanoes were Tungurahua (Ecuador) and Nevado del Huila (Colombia). The TC4 data provide rare insight into the chemistry of volcanic plumes in the tropical troposphere and permit a comparison of SO2 column amounts measured by the Ozone Monitoring Instrument (OMI) on the Aura satellite with in situ SO2 measurements. Elevated concentrations of SO2, sulfate aerosol, and particles were measured by DC‐8 instrumentation in volcanic outflow at altitudes of 3–6 km. Estimated plume ages range from ∼2 h at Huila to ∼22–48 h downwind of Ecuador. The plumes contained sulfate‐rich accumulation mode particles that were variably neutralized and often highly acidic. A significant fraction of supermicron volcanic ash was evident in one plume. In‐plume O3 concentrations were ∼70%–80% of ambient levels downwind of Ecuador, but data are insufficient to ascribe this to O3 depletion via reactive halogen chemistry. The TC4 data record rapid cloud processing of the Huila volcanic plume involving aqueous‐phase oxidation of SO2 by H2O2, but overall the data suggest average in‐plume SO2 to sulfate conversion rates of ∼1%–2% h−1 . SO2 column amounts measured in the Tungurahua plume (∼0.1–0.2 Dobson units) are commensurate with average SO2 columns retrieved from OMI measurements in the volcanic outflow region in July 2007. The TC4 data set provides further evidence of the impact of volcanic emissions on tropospheric acidity and oxidizing capacit