876 research outputs found
Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide
This paper presents an analytical system for analysis of all single
substituted isotopologues (<sup>12</sup>C<sup>16</sup>O<sup>17</sup>O,
<sup>12</sup>C<sup>16</sup>O<sup>18</sup>O, <sup>13</sup>C<sup>16</sup>O<sup>16</sup>O) in nanomolar quantities
of CO<sub>2</sub> extracted from stratospheric air samples. CO<sub>2</sub> is
separated from bulk air by gas chromatography and CO<sub>2</sub> isotope ratio
measurements (ion masses 45 / 44 and 46 / 44) are performed using isotope ratio
mass spectrometry (IRMS). The <sup>17</sup>O excess (Î<sup>17</sup>O) is
derived from isotope measurements on two different CO<sub>2</sub> aliquots:
unmodified CO<sub>2</sub> and CO<sub>2</sub> after complete oxygen isotope exchange with
cerium oxide (CeO<sub>2</sub>) at 700 °C. Thus, a single measurement of
Î<sup>17</sup>O requires two injections of 1 mL of air with a CO<sub>2</sub>
mole fraction of 390 Îźmol mol<sup>â1</sup> at 293 K and 1 bar pressure
(corresponding to 16 nmol CO<sub>2</sub> each). The required sample size
(including flushing) is 2.7 mL of air. A single analysis (one pair of
injections) takes 15 minutes. The analytical system is fully automated for
unattended measurements over several days. The standard deviation of the
<sup>17</sup>O excess analysis is 1.7‰. Multiple
measurements on an air sample reduce the measurement uncertainty, as
expected for the statistical standard error. Thus, the uncertainty for a
group of 10 measurements is 0.58‰ for Δ
<sup>17</sup>O in 2.5 h of analysis. 100 repeat analyses of one air sample
decrease the standard error to 0.20‰. The instrument
performance was demonstrated by measuring CO<sub>2</sub> on stratospheric air
samples obtained during the EU project RECONCILE with the high-altitude
aircraft Geophysica. The precision for RECONCILE data is 0.03‰ (1σ) for δ<sup>13</sup>C, 0.07‰ (1σ) for δ<sup>18</sup>O and 0.55‰ (1σ) for δ<sup>17</sup>O for a sample of 10
measurements. This is sufficient to examine stratospheric enrichments, which
at altitude 33 km go up to 12‰ for δ<sup>17</sup>O
and up to 8‰ for δ<sup>18</sup>O with respect to
tropospheric CO<sub>2</sub> : δ<sup>17</sup>O ~
21‰ Vienna Standard Mean Ocean Water (VSMOW), δ<sup>18</sup>O ~
41‰ VSMOW (Lämmerzahl et al., 2002). The samples
measured with our analytical technique agree with available data for
stratospheric CO<sub>2</sub>
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Using Nanoparticle X-ray Spectroscopy to Probe the Formation of Reactive Chemical Gradients in Diffusion-Limited Aerosols.
For aerosol particles that exist in highly viscous, diffusion-limited states, steep chemical gradients are expected to form during photochemical aging in the atmosphere. Under these conditions, species at the aerosol surface are more rapidly transformed than molecules residing in the particle interior. To examine the formation and evolution of chemical gradients at aerosol interfaces, the heterogeneous reaction of hydroxyl radicals (OH) on âź200 nm particles of pure squalane (a branched, liquid hydrocarbon) and octacosane (a linear, solid hydrocarbon) and binary mixtures of the two are used to understand how diffusion limitations and phase separation impact the particle reactivity. Aerosol mass spectrometry is used to measure the effective heterogeneous OH uptake coefficient (Îłeff) and oxidation kinetics in the bulk, which are compared with the elemental composition of the surface obtained using X-ray photoemission. When diffusion rates are fast relative to the reaction frequency, as is the case for squalane and low-viscosity squalane-octacosane mixtures, the reaction is efficient (Îłeff âź 0.3) and only limited by the arrival of OH to the interface. However, for cases, where the diffusion rates are slower than reaction rates, as in pure octacosane and higher-viscosity squalane-octacosane mixtures, the heterogeneous reaction occurs in a mixing-limited regime and is âź10Ă slower (Îłeff âź 0.03). This is in contrast to carbon and oxygen K edge X-ray absorption measurements that show that the octacosane interface is oxidized much more rapidly than that of pure squalane particles. The O/C ratio of the surface (estimated to be the top 6-8 nm of the interface) is measured to change with rate constants of (3.0 Âą 0.9) Ă 10-13 and (8.6 Âą 1.2) Ă 10-13 cm3 molecule-1 s-1 for squalane and octacosane particles, respectively. The differences in surface oxidation rates are analyzed using a previously published reaction-diffusion model, which suggests that a 1-2 nm highly oxidized crust forms on octacosane particles, whereas in pure squalane, the reaction products are homogeneously mixed within the aerosol. This work illustrates how diffusion limitations can form particles with highly oxidized surfaces even at relatively low oxidant exposures, which is in turn expected to influence their microphysics in the atmosphere
Multiple solutions of the quasirelativistic Choquard equation
We prove existence of multiple solutions to the quasirelativistic Choquard equation with a scalar potential
Assessing TMS-induced D and I waves with spinal H-reflexes
Transcranial magnetic stimulation (TMS) of motor cortex produces a series of descending volleys known as D (direct) and I (indirect) waves. In the present study, we questioned whether spinal H-reflexes can be used to dissect D waves and early and late I waves from TMS. We therefore probed H-reflex facilitation at arrival times of D and I waves at the spinal level and thereby changed TMS parameters that have previously been shown to have selective effects on evoked D and different I waves. We changed TMS intensity and current direction and applied a double-pulse paradigm known as short-interval intracortical inhibition (SICI). Experiments were conducted in flexor carpi radialis (FCR) in the arm and soleus (SOL) in the leg. There were two major findings: 1) in FCR, H-reflex facilitation showed characteristic modulations with altered TMS parameters that correspond to the changes of evoked D and I waves; and 2) H-reflexes in SOL did not, possibly because of increased interference from other spinal circuits. Therefore, the most significant outcome of this study is that in FCR, H-reflexes combined with TMS seem to be a useful technique to dissect TMS-induced D and I waves. NEW & NOTEWORTHY Questions that relate to corticospinal function in pathophysiology and movement control demand sophisticated techniques to provide information about corticospinal mechanisms. We introduce a noninvasive electrophysiological technique that may be useful in describing such mechanisms in more detail by dissecting D and I waves from transcranial magnetic stimulation (TMS). Based on the combination of spinal H-reflexes and TMS in the flexor carpi radialis muscle, the technique was shown to measure selective effects on D and I waves from changing TMS parameters
Thermodynamic properties of confined interacting Bose gases - a renormalization group approach
A renormalization group method is developed with which thermodynamic
properties of a weakly interacting, confined Bose gas can be investigated.
Thereby effects originating from a confining potential are taken into account
by periodic boundary conditions and by treating the resulting discrete energy
levels of the confined degrees of freedom properly. The resulting density of
states modifies the flow equations of the renormalization group in momentum
space. It is shown that as soon as the characteristic length of confinement
becomes comparable to the thermal wave length of a weakly interacting and
trapped Bose gas its thermodynamic properties are changed significantly. This
is exemplified by investigating characteristic bunching properties of the
interacting Bose gas which manifest themselves in the second order coherence
factor
Single polymer adsorption in shear: flattening versus hydrodynamic lift and corrugation effects
The adsorption of a single polymer to a flat surface in shear is investigated
using Brownian hydrodynamics simulations and scaling arguments. Competing
effects are disentangled: in the absence of hydrodynamic interactions, shear
drag flattens the chain and thus enhances adsorption. Hydrodynamic lift on the
other hand gives rise to long-ranged repulsion from the surface which preempts
the surface-adsorbed state via a discontinuous desorption transition, in
agreement with theoretical arguments. Chain flattening is dominated by
hydrodynamic lift, so overall, shear flow weakens the adsorption of flexible
polymers. Surface friction due to small-wavelength surface potential
corrugations is argued to weaken the surface attraction as well.Comment: 6 pages, 4 figure
Path Integral Approach to the Non-Relativistic Electron Charge Transfer
A path integral approach has been generalized for the non-relativistic
electron charge transfer processes. The charge transfer - the capture of an
electron by an ion passing another atom or more generally the problem of
rearrangement collisions is formulated in terms of influence functionals. It
has been shown that the electron charge transfer process can be treated either
as electron transition problem or as elastic scattering of ion and atom in the
some effective potential field. The first-order Born approximation for the
electron charge transfer cross section has been reproduced to prove the
adequacy of the path integral approach for this problem.Comment: 19 pages, 1 figure, to appear in Journal of Physics B: Atomic,
Molecular & Optical, vol.34, 200
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