Systematic reduction of complex tropospheric chemical mechanisms, Part I: sensitivity and time-scale analyses

International audienceExplicit mechanisms describing the complex degradation pathways of atmospheric volatile organic compounds (VOCs) are important, since they allow the study of the contribution of individual VOCS to secondary pollutant formation. They are computationally expensive to solve however, since they contain large numbers of species and a wide range of time-scales causing stiffness in the resulting equation systems. This paper and the following companion paper describe the application of systematic and automated methods for reducing such complex mechanisms, whilst maintaining the accuracy of the model with respect to important species and features. The methods are demonstrated via application to version 2 of the Leeds Master Chemical Mechanism. The methods of Jacobian analysis and overall rate sensitivity analysis proved to be efficient and capable of removing the majority of redundant reactions and species in the scheme across a wide range of conditions relevant to the polluted troposphere. The application of principal component analysis of the rate sensitivity matrix was computationally expensive due to its use of the decomposition of very large matrices, and did not produce significant reduction over and above the other sensitivity methods. The use of the quasi-steady state approximation (QSSA) proved to be an extremely successful method of removing the fast time-scales within the system, as demonstrated by a local perturbation analysis at each stage of reduction. QSSA species were automatically selected via the calculation of instantaneous QSSA errors based on user-selected tolerances. The application of the QSSA led to the removal of a large number of alkoxy radicals and excited Criegee bi-radicals via reaction lumping. The resulting reduced mechanism was shown to reproduce the concentration profiles of the important species selected from the full mechanism over a wide range of conditions, including those outside of which the reduced mechanism was generated. As a result of a reduction in the number of species in the scheme of a factor of 2, and a reduction in stiffness, the computational time required for simulations was reduced by a factor of 4 when compared to the full scheme

Systematic reduction of complex tropospheric chemical mechanisms, Part II: Lumping using a time-scale based approach

This paper presents a formal method of species lumping that can be applied automatically to intermediate compounds within detailed and complex tropospheric chemical reaction schemes. The method is based on grouping species with reference to their chemical lifetimes and reactivity structures. A method for determining the forward and reverse transformations between individual and lumped compounds is developed. Preliminary application to the Leeds Master Chemical Mechanism (MCMv2.0) has led to the removal of 734 species and 1777 reactions from the scheme, with minimal degradation of accuracy across a wide range of test trajectories relevant to polluted tropospheric conditions. The lumped groups are seen to relate to groups of peroxy acyl nitrates, nitrates, carbonates, oxepins, substituted phenols, oxeacids and peracids with similar lifetimes and reaction rates with OH. In combination with other reduction techniques, such as sensitivity analysis and the application of the quasi-steady state approximation (QSSA), a reduced mechanism has been developed that contains 35% of the number of species and 40% of the number of reactions compared to the full mechanism. This has led to a speed up of a factor of 8 in terms of computer calculation time within box model simulations

Systematic reduction of complex tropospheric chemical mechanisms using sensitivity and time-scale analyses

International audienceExplicit mechanisms describing the complex degradation pathways of atmospheric volatile organic compounds (VOCs) are important, since they allow the study of the contribution of individual VOCS to secondary pollutant formation. They are computationally expensive to solve however, since they contain large numbers of species and a wide range of time-scales causing stiffness in the resulting equation systems. This paper and the following companion paper describe the application of systematic and automated methods for reducing such complex mechanisms, whilst maintaining the accuracy of the model with respect to important species and features. The methods are demonstrated via application to version 2 of the Leeds Master Chemical Mechanism. The methods of local concentration sensitivity analysis and overall rate sensitivity analysis proved to be efficient and capable of removing the majority of redundant reactions and species in the scheme across a wide range of conditions relevant to the polluted troposphere. The application of principal component analysis of the rate sensitivity matrix was computationally expensive due to its use of the decomposition of very large matrices, and did not produce significant reduction over and above the other sensitivity methods. The use of the quasi-steady state approximation (QSSA) proved to be an extremely successful method of removing the fast time-scales within the system, as demonstrated by a local perturbation analysis at each stage of reduction. QSSA species were automatically selected via the calculation of instantaneous QSSA errors based on user-selected tolerances. The application of the QSSA led to the removal of a large number of alkoxy radicals and excited Criegee bi-radicals via reaction lumping. The resulting reduced mechanism was shown to reproduce the concentration profiles of the important species selected from the full mechanism over a wide range of conditions, including those outside of which the reduced mechanism was generated. As a result of a reduction in the number of species in the scheme of a factor of 2, and a reduction in stiffness, the computational time required for simulations was reduced by a factor of 4 when compared to the full scheme

Systematic lumping of complex tropospheric chemical mechanisms using a time-scale based approach

International audienceThis paper presents a formal method of species lumping that can be applied automatically to intermediate compounds within detailed and complex tropospheric chemical reaction schemes. The method is based on grouping species with reference to their chemical lifetimes and reactivity structures. A method for determining the forward and reverse transformations between individual and lumped compounds is developed. Preliminary application to the Leeds Master Chemical Mechanism (MCMv2.0) has led to the removal of 734 species and 1777 reactions from the scheme, with minimal degradation of accuracy across a wide range of test trajectories relevant to polluted tropospheric conditions. The lumped groups are seen to relate to groups of peroxy acyl nitrates, nitrates, carbonates, oxepins, substituted phenols, oxeacids and peracids with similar lifetimes and reaction rates with OH. In combination with other reduction techniques, such as sensitivity analysis and the application of the quasi-steady state approximation (QSSA), a reduced mechanism has been developed that contains 35% of the number of species and 40% of the number of reactions compared to the full mechanism. This has led to a speed up of a factor of 8 in terms of computer calculation time within box model simulations

Effects of etelcalcetide on fibroblast growth factor 23 in patients with secondary hyperparathyroidism receiving hemodialysis

Background: Etelcalcetide is an intravenous calcimimetic approved for treatment of secondary hyperparathyroidism (sHPT) in patients receiving hemodialysis. Besides lowering parathyroid hormone (PTH), etelcalcetide also significantly reduces fibroblast growth factor 23 (FGF23), but the mechanisms are unknown. Methods: To investigate potential mediators of etelcalcetide-induced FGF23 reduction, we performed secondary analyses of the 26-week randomized trials that compared the effects on PTH of etelcalcetide (n = 509) versus placebo (n = 514) and etelcalcetide (n = 340) versus cinacalcet (n = 343) in adults with sHPT receiving hemodialysis. We analyzed changes in FGF23 in relation to changes in PTH, calcium, phosphate and bone turnover markers. We also investigated how concomitant treatments aimed at mitigating hypocalcemia altered the FGF23-lowering effects of etelcalcetide. Results: Etelcalcetide reduced FGF23 [median % change (quartile 1-quartile 3)] from baseline to the end of the trial significantly more than placebo [-56% (-85 to -7) versus +2% (-40 to +65); P < 0.001] and cinacalcet [-68% (-87 to -26) versus -41% (-76 to +25); P < 0.001]. Reductions in FGF23 correlated strongly with reductions in calcium and phosphate, but not with PTH; correlations with bone turnover markers were inconsistent and of borderline significance. Increases in concomitant vitamin D administration partially attenuated the FGF23-lowering effect of etelcalcetide, but increased dialysate calcium concentration versus no increase and increased dose of calcium supplementation versus no increase did not attenuate the FGF23-lowering effects of etelcalcetide. Conclusion: These data suggest that etelcalcetide potently lowers FGF23 in patients with sHPT receiving hemodialysis and that the effect remains detectable among patients who receive concomitant treatments aimed at mitigating treatment-associated decreases in serum calcium

A no-singularity scenario in loop quantum gravity

Canonical methods allow the derivation of effective gravitational actions from the behavior of space-time deformations reflecting general covariance. With quantum effects, the deformations and correspondingly the effective actions change, revealing dynamical implications of quantum corrections. A new systematic way of expanding these actions is introduced showing as a first result that inverse-triad corrections of loop quantum gravity simplify the asymptotic dynamics near a spacelike collapse singularity. By generic quantum effects, the singularity is removed.Comment: 10 page

Half-life and spin of 60Mn^g

A value of 0.28 +/- 0.02 s has been deduced for the half-life of the ground state of 60Mn, in sharp contrast to the previously adopted value of 51 +/- 6 s. Access to the low-spin 60Mn ground state was accomplished via beta decay of the 0+ 60Cr parent nuclide. New, low-energy states in 60Mn have been identified from beta-delayed gamma-ray spectroscopy. The new, shorter half-life of 60Mn^g is not suggestive of isospin forbidden beta decay, and new spin and parity assignments of 1+ and 4+ have been adopted for the ground and isomeric beta-decaying states, respectively, of 60Mn.Comment: 13 pages, 5 figures, Accepted for publication in Phys. Rev.

Probing shell structure and shape changes in neutron-rich sulfur isotopes through transient-field g factor measurements on fast radioactive beams of 38S and 40S

The shell structure underlying shape changes in neutron-rich nuclei near N=28 has been investigated by a novel application of the transient field technique to measure the first-excited state g factors in 38S and 40S produced as fast radioactive beams. There is a fine balance between proton and neutron contributions to the magnetic moments in both nuclei. The g factor of deformed 40S does not resemble that of a conventional collective nucleus because spin contributions are more important than usual.Comment: 10 pages, 6 figures, accepted in PR