Evaluating ozone depletion from very short-lived halocarbons

A new approach is needed for calculating the ozone depletion potential (ODP) of short-lived gases with mean lifetimes less than 100 days. Clearly, the ozone loss from such gases depends strongly on the location and season of emissions. It is proposed that delivery to the tropical tropopause is a surrogate for the amount of halogen entering the stratosphere. Thus 3-D global models, with accurate simulation of tropospheric chemistry and transport, can calculate the ODP specific to tropical sources (high) and high-latitude sources (low). The ODP of CH2BrCH2CH3  from this analysis ranges from 0.0002 to 0.06 depending on the location and season of emissions

Periods and Feynman integrals

We consider multi-loop integrals in dimensional regularisation and the corresponding Laurent series. We study the integral in the Euclidean region and where all ratios of invariants and masses have rational values. We prove that in this case all coefficients of the Laurent series are periods.Comment: 22 pages, appendix added, version to be publishe

Observed OH and HO_2 in the upper troposphere suggest a major source from convective injection of peroxides

ER-2 aircraft observations of OH and HO_2 concentrations in the upper troposphere during the NASA/STRAT campaign are interpreted using a photochemical model constrained by local observations of O_3, H_2O, NO, CO, hydrocarbons, albedo and overhead ozone column. We find that the reaction Q(^(1)D) + H_2O is minor compared to acetone photolysis as a primary source of HO_x (= OH + peroxy radicals) in the upper troposphere. Calculations using a diel steady state model agree with observed HO_x concentrations in the lower stratosphere and, for some flights, in the upper troposphere. However, for other flights in the upper troposphere, the steady state model underestimates observations by a factor of 2 or more. These model underestimates are found to be related to a recent (< 1 week) convective origin of the air. By conducting time-dependent model calculations along air trajectories determined for the STRAT flights, we show that convective injection of CH_3OOH and H_2O_2 from the boundary layer to the upper troposphere could resolve the discrepancy. These injections of HO_x reservoirs cause large HO_x increases in the tropical upper troposphere for over a week downwind of the convective activity. We propose that this mechanism provides a major source of HO_x in the upper troposphere. Simultaneous measurements of peroxides, formaldehyde and acetone along with OH and HO_2 are needed to test our hypothesis

The cone of curves and the Cox ring of rational surfaces given by divisorial valuations

We consider surfaces X defined by plane divisorial valuations v of the quotient field of the local ring R at a closed point p of the projective plane P-2 over an arbitrary algebraically closed field k and centered at R. We prove that the regularity of the cone of curves of X is equivalent to the fact that v is non-positive on Op(2) (P-2 \ L), where L is a certain line containing p. Under these conditions, we characterize when the characteristic cone of X is closed and its Cox ring finitely generated. Equivalent conditions to the fact that v is negative on Opt (P-2 \ L) k are also given. (C) 2015 Published by Elsevier Inc.Supported by Spain Ministry of Economy MTM2012-36917-C03-03 and Universitat Jaume I P1-1B201502.Galindo Pastor, C.; Monserrat Delpalillo, FJ. (2016). The cone of curves and the Cox ring of rational surfaces given by divisorial valuations. Advances in Mathematics. 290:1040-1061. https://doi.org/10.1016/j.aim.2015.12.015S1040106129

Role of regional wetland emissions in atmospheric methane variability

Atmospheric methane (CH4) accounts for ~20% of the total direct anthropogenic radiative forcing by long-lived greenhouse gases. Surface observations show a pause (1999-2006) followed by a resumption in CH4 growth, which remain largely unexplained. Using a land surface model, we estimate wetland CH4 emissions from 1993 to 2014 and study the regional contributions to changes in atmospheric CH4. Atmospheric model simulations using these emissions, together with other sources, compare well with surface and satellite CH4 data. Modelled global wetland emissions vary by ±3%/yr (σ=4.8 Tg), mainly due to precipitation-induced changes in wetland area, but the integrated effect makes only a small contribution to the pause in CH4 growth from 1999 to 2006. Increasing temperature, which increases wetland area, drives a long-term trend in wetland CH4 emissions of +0.2%/yr (1999 to 2014). The increased growth post-2006 was partly caused by increased wetland emissions (+3%), mainly from Tropical Asia, Sourthern Africa and Australia

Statistical inference of OH concentrations and air mass dilution rates from successive observations of non-methane hydrocarbons in single air masses

Bayesian inference has been used to determine rigorous estimates of hydroxyl radical concentrations () and air mass dilution rates (K) averaged following air masses between linked observations of nonmethane hydrocarbons (NMHCs) spanning the North Atlantic during the Intercontinental Transport and Chemical Transformation (ITCT)-Lagrangian-2K4 experiment. The Bayesian technique obtains a refined (posterior) distribution of a parameter given data related to the parameter through a model and prior beliefs about the parameter distribution. Here, the model describes hydrocarbon loss through OH reaction and mixing with a background concentration at rate K. The Lagrangian experiment provides direct observations of hydrocarbons at two time points, removing assumptions regarding composition or sources upstream of a single observation. The estimates are sharpened by using many hydrocarbons with different reactivities and accounting for their variability and measurement uncertainty. A novel technique is used to construct prior background distributions of many species, described by variation of a single parameter . This exploits the high correlation of species, related by the first principal component of many NMHC samples. The Bayesian method obtains posterior estimates of , K and following each air mass. Median values are typically between 0.5 and 2.0 × 106 molecules cm−3, but are elevated to between 2.5 and 3.5 × 106 molecules cm−3, in low-level pollution. A comparison of estimates from absolute NMHC concentrations and NMHC ratios assuming zero background (the “photochemical clock” method) shows similar distributions but reveals systematic high bias in the estimates from ratios. Estimates of K are ∼0.1 day−1 but show more sensitivity to the prior distribution assumed

Observed OH and HO2 in the upper troposphere suggest a major source from convective injection of peroxides

ER-2 aircraft observations of OH and HO2 concentrations in the upper troposphere during the NASA/STRAT campaign are interpreted using a photochemical model constrained by local observations of O3, H2O, NO, CO, hydrocarbons, albedo and overhead ozone column. We find that the reaction Q(¹D) + H2O is minor compared to acetone photolysis as a primary source of HOx (= OH + peroxy radicals) in the upper troposphere. Calculations using a diel steady state model agree with observed HOx concentrations in the lower stratosphere and, for some flights, in the upper troposphere. However, for other flights in the upper troposphere, the steady state model underestimates observations by a factor of 2 or more. These model underestimates are found to be related to a recent (< 1 week) convective origin of the air. By conducting time-dependent model calculations along air trajectories determined for the STRAT flights, we show that convective injection of CH3OOH and H2O2 from the boundary layer to the upper troposphere could resolve the discrepancy. These injections of HOx reservoirs cause large HOx increases in the tropical upper troposphere for over a week downwind of the convective activity. We propose that this mechanism provides a major source of HOx in the upper troposphere. Simultaneous measurements of peroxides, formaldehyde and acetone along with OH and HO2 are needed to test our hypothesis.Engineering and Applied Science

Rising atmospheric methane: 2007-2014 growth and isotopic shift

From 2007 to 2013, the globally averaged mole fraction of methane in the atmosphere increased by 5.7±1.2ppb yr$^{-1}$. Simultaneously, $\delta^{13}$C$_\text{CH4}$ (a measure of the $^{13}$C/$^{12}$C isotope ratio in methane) has shifted to significantly more negative values since 2007. Growth was extreme in 2014, at 12.5±0.4ppb, with a further shift to more negative values being observed at most latitudes. The isotopic evidence presented here suggests that the methane rise was dominated by significant increases in biogenic methane emissions, particularly in the tropics, for example, from expansion of tropical wetlands in years with strongly positive rainfall anomalies or emissions from increased agricultural sources such as ruminants and rice paddies. Changes in the removal rate of methane by the OH radical have not been seen in other tracers of atmospheric chemistry and do not appear to explain short-term variations in methane. Fossil fuel emissions may also have grown, but the sustained shift to more $^{13}$C-depleted values and its significant interannual variability, and the tropical and Southern Hemisphere loci of post-2007 growth, both indicate that fossil fuel emissions have not been the dominant factor driving the increase. A major cause of increased tropical wetland and tropical agricultural methane emissions, the likely major contributors to growth, may be their responses to meteorological change.This work was supported by the UK Natural Environment Research Council projects NE/N016211/1 The Global Methane Budget, NE/M005836/1 Methane at the edge, NE/K006045/1 The Southern Methane Anomaly and NE/I028874/1 MAMM. We thank the UK Meteorological Office for flask collection and hosting the continuous measurement at Ascension, the Ascension Island Government for essential support, and Thumeka Mkololo for flask collection in Cape Tow

Oceanic uptake and the global atmospheric acetone budget

In this study, direct measurements of the air/ sea flux of acetone were made over the North Pacific Ocean. The results demonstrate that the net flux of acetone is into, rather than out of the oceans. The extrapolated global ocean uptake of 48 Tg yr(-1) requires a major revision of the atmospheric acetone budget. This result is consistent with a recent reevaluation of acetone photodissociation quantum yields

Factors regulating ozone over the United States and its export to the global atmosphere

The factors regulating summertime O3 over the United States and its export to the global atmosphere are examined with a 3-month simulation using a continental scale, three-dimensional photochemical model. It is found that reducing NOx emissions by 50% from 1985 levels would decrease rural O3 concentrations over the eastern United States by about 15% under almost all meteorological conditions, while reducing anthropogenic hydrocarbon emissions by 50% would have less than a 4% effect except in the largest urban plumes. The strongly NOx-limited conditions in the model reflect the dominance of rural areas as sources of O3 on the regional scale. The correlation between O3 concentrations and temperature observed at eastern U.S. sites is attributed in part to the association of high temperatures with regional stagnation, and in part to an actual dependence of O3 production on temperature driven primarily by conversion of NOx to peroxyacetylnitrate (PAN). The net number of O3 molecules produced per molecule of NOx consumed (net O3 production efficiency, accounting for both chemical production and chemical loss of O3) has a mean value of 6.3 in the U.S. boundary layer; it is 3 times higher in the western United States than in the east because of lower NOx concentrations in the west. Approximately 70% of the net chemical production of O3 in the U.S. boundary layer is exported (the rest is deposited). Only 6% of the NOx emitted in the United States is exported out of the U.S. boundary layer as NOx or PAN, but this export contributes disproportionately to total U.S. influence on global tropospheric O3because of the high O3 production efficiency per unit NOx in the remote troposphere. It is estimated that export of U.S. pollution supplies 8 Gmol O3 d−1 to the global troposphere in summer, including 4 Gmol d−1 from direct export of O3 out of the U.S. boundary layer and 4 Gmol d−1 from production of O3 downwind of the United States due to exported NOx. This U.S. pollution source can be compared to estimates of 18–28 Gmol d−1 for the cross-tropopause transport of O3 over the entire northern hemisphere in summer