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 (¹²C¹⁶O¹⁷O, ¹²C¹⁶O¹⁸O, ¹³C¹⁶O¹⁶O) in nanomolar quantities of CO₂ extracted from stratospheric air samples. CO₂ is separated from bulk air by gas chromatography and CO₂ isotope ratio measurements (ion masses 45 / 44 and 46 / 44) are performed using isotope ratio mass spectrometry (IRMS). The ¹⁷O excess (Δ¹⁷O) is derived from isotope measurements on two different CO₂ aliquots: unmodified CO₂ and CO₂ after complete oxygen isotope exchange with cerium oxide (CeO₂) at 700 °C. Thus, a single measurement of Δ¹⁷O requires two injections of 1 mL of air with a CO₂ mole fraction of 390 μmol mol⁻¹ at 293 K and 1 bar pressure (corresponding to 16 nmol CO₂ 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 ¹⁷O 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 ¹⁷O 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 CO₂ 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 δ¹³C, 0.07‰ (1σ) for δ¹⁸O and 0.55‰ (1σ) for δ¹⁷O for a sample of 10 measurements. This is sufficient to examine stratospheric enrichments, which at altitude 33 km go up to 12‰ for δ¹⁷O and up to 8‰ for δ¹⁸O with respect to tropospheric CO₂ : δ¹⁷O ~ 21‰ Vienna Standard Mean Ocean Water (VSMOW), δ¹⁸O ~ 41‰ VSMOW (Lämmerzahl et al., 2002). The samples measured with our analytical technique agree with available data for stratospheric CO₂

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

Entropy, time irreversibility and Schroedinger equation in a primarily discrete space-time

In this paper we show that the existence of a primarily discrete space-time may be a fruitful assumption from which we may develop a new approach of statistical thermodynamics in pre-relativistic conditions. The discreetness of space-time structure is determined by a condition that mimics the Heisenberg uncertainty relations and the motion in this space-time model is chosen as simple as possible. From these two assumptions we define a path-entropy that measures the number of closed paths associated with a given energy of the system preparation. This entropy has a dynamical character and depends on the time interval on which we count the paths. We show that it exists an like-equilibrium condition for which the path-entropy corresponds exactly to the usual thermodynamic entropy and, more generally, the usual statistical thermodynamics is reobtained. This result derived without using the Gibbs ensemble method shows that the standard thermodynamics is consistent with a motion that is time-irreversible at a microscopic level. From this change of paradigm it becomes easy to derive a $H-theorem$. A comparison with the traditional Boltzmann approach is presented. We also show how our approach can be implemented in order to describe reversible processes. By considering a process defined simultaneously by initial and final conditions a well defined stochastic process is introduced and we are able to derive a Schroedinger equation, an example of time reversible equation.Comment: latex versio

Why is the DNA Denaturation Transition First Order?

We study a model for the denaturation transition of DNA in which the molecules are considered as composed of a sequence of alternating bound segments and denaturated loops. We take into account the excluded-volume interactions between denaturated loops and the rest of the chain by exploiting recent results on scaling properties of polymer networks of arbitrary topology. The phase transition is found to be first order in d=2 dimensions and above, in agreement with experiments and at variance with previous theoretical results, in which only excluded-volume interactions within denaturated loops were taken into account. Our results agree with recent numerical simulations.Comment: Revised version. To appear in Phys. Rev. Let

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

Polyelectrolyte multilayer formation: electrostatics and short-range interactions

We investigate the phenomenon of multilayer formation via layer-by-layer deposition of alternating charge polyelectrolytes. Using mean-field theory, we find that a strong short-range attraction between the two types of polymer chains is essential for the formation of multilayers. The dependence of the required short-range attraction on the polymer charge fraction and salt concentration is calculated. For weak short-range attraction between any two adjacent layers, the adsorbed amount (per added layer) decays as the distance from the surface increases, until the chains stop adsorbing altogether. For strong short-range attraction, the adsorbed amount per layer increases after an initial decrease, and finally it stabilizes in the form of a polyelectrolyte multilayer that can be repeated many times.Comment: 8 pages, 7 figure

Statistical Mechanics of Membrane Protein Conformation: A Homopolymer Model

The conformation and the phase diagram of a membrane protein are investigated via grand canonical ensemble approach using a homopolymer model. We discuss the nature and pathway of $\alpha$-helix integration into the membrane that results depending upon membrane permeability and polymer adsorptivity. For a membrane with the permeability larger than a critical value, the integration becomes the second order transition that occurs at the same temperature as that of the adsorption transition. For a nonadsorbing membrane, the integration is of the first order due to the aggregation of $\alpha$-helices.Comment: RevTeX with 5 postscript figure

A core outcome set for localised prostate cancer effectiveness trials

Objective: To develop a core outcome set (COS) applicable for effectiveness trials of all interventions for localised prostate cancer. Background: Many treatments exist for localised prostate cancer, although it is unclear which offers the optimal therapeutic ratio. This is confounded by inconsistencies in the selection, definition, measurement and reporting of outcomes in clinical trials. Subjects and methods: A list of 79 outcomes was derived from a systematic review of published localised prostate cancer effectiveness studies and semi-structured interviews with 15 prostate cancer patients. A two-stage consensus process involving 118 patients and 56 international healthcare professionals (HCPs) (cancer specialist nurses, urological surgeons and oncologists) was undertaken, consisting of a three-round Delphi survey followed by a face-to-face consensus panel meeting of 13 HCPs and 8 patients. Results: The final COS included 19 outcomes. Twelve apply to all interventions: death from prostate cancer, death from any cause, local disease recurrence, distant disease recurrence/metastases, disease progression, need for salvage therapy, overall quality of life, stress urinary incontinence, urinary function, bowel function, faecal incontinence, sexual function. Seven were intervention-specific: perioperative deaths (surgery), positive surgical margin (surgery), thromboembolic disease (surgery), bothersome or symptomatic urethral or anastomotic stricture (surgery), need for curative treatment (active surveillance), treatment failure (ablative therapy), and side effects of hormonal therapy (hormone therapy). The UK-centric participants may limit the generalisability to other countries, but trialists should reason why the COS would not be applicable. The default position should not be that a COS developed in one country will automatically not be applicable elsewhere. Conclusion: We have established a COS for trials of effectiveness in localised prostate cancer, applicable across all interventions which should be measured in all localised prostate cancer effectiveness trials

Some approximate analytical methods in the study of the self-avoiding loop model with variable bending rigidity and the critical behaviour of the strong coupling lattice Schwinger model with Wilson fermions

Some time ago Salmhofer demonstrated the equivalence of the strong coupling lattice Schwinger model with Wilson fermions to a certain 8-vertex model which can be understood as a self-avoiding loop model on the square lattice with bending rigidity $\eta = 1/2$ and monomer weight $z = (2\kappa)^{-2}$. The present paper applies two approximate analytical methods to the investigation of critical properties of the self-avoiding loop model with variable bending rigidity, discusses their validity and makes comparison with known MC results. One method is based on the independent loop approximation used in the literature for studying phase transitions in polymers, liquid helium and cosmic strings. The second method relies on the known exact solution of the self-avoiding loop model with bending rigidity $\eta = 1/\sqrt{2}$. The present investigation confirms recent findings that the strong coupling lattice Schwinger model becomes critical for $\kappa_{cr} \simeq 0.38-0.39$. The phase transition is of second order and lies in the Ising model universality class. Finally, the central charge of the strong coupling Schwinger model at criticality is discussed and predicted to be $c = 1/2$.Comment: 22 pages LaTeX, 6 Postscript figure