Optimisation of Quantum Trajectories Driven by Strong-field Waveforms

Quasi-free field-driven electron trajectories are a key element of strong-field dynamics. Upon recollision with the parent ion, the energy transferred from the field to the electron may be released as attosecond duration XUV emission in the process of high harmonic generation (HHG). The conventional sinusoidal driver fields set limitations on the maximum value of this energy transfer, and it has been predicted that this limit can be significantly exceeded by an appropriately ramped-up cycleshape. Here, we present an experimental realization of such cycle-shaped waveforms and demonstrate control of the HHG process on the single-atom quantum level via attosecond steering of the electron trajectories. With our optimized optical cycles, we boost the field-ionization launching the electron trajectories, increase the subsequent field-to-electron energy transfer, and reduce the trajectory duration. We demonstrate, in realistic experimental conditions, two orders of magnitude enhancement of the generated XUV flux together with an increased spectral cutoff. This application, which is only one example of what can be achieved with cycle-shaped high-field light-waves, has farreaching implications for attosecond spectroscopy and molecular self-probing

Decreasing seasonal cycle amplitude of methane in the northern high latitudes being driven by lower-latitude changes in emissions and transport

Atmospheric methane (CH4) concentrations are rising, which are expected to lead to a corresponding increase in the global seasonal cycle amplitude (SCA) – the difference between its seasonal maximum and minimum values. The reaction between CH4 and its main sink, OH, is dependent on the amount of CH4 and OH in the atmosphere. The concentration of OH varies seasonally, and due to the increasing burden of CH4 in the atmosphere, it is expected that the SCA of CH4 will increase due to the increased removal of CH4 through a reaction with OH in the atmosphere. Spatially varying changes in the SCA could indicate long-term persistent variations in the seasonal sources and sinks, but such SCA changes have not been investigated. Here we use surface flask measurements and a 3D chemical transport model (TOMCAT) to diagnose changes in the SCA of atmospheric CH4 between 1995–2020 and attribute the changes regionally to contributions from different sectors. We find that the observed SCA decreased by 4 ppb (7.6 %) in the northern high latitudes (NHLs; 60–90∘ N), while the SCA increased globally by 2.5 ppb (6.5 %) during this time period. TOMCAT reproduces the change in the SCA at observation sites across the globe. Therefore, we use it to attribute regions which are contributing to the changes in the NHL SCA, which shows an unexpected change in the SCA that differs from the rest of the world. We find that well-mixed background CH4, likely from emissions originating in, and transported from, more southerly latitudes has the largest impact on the decreasing SCA in the NHLs (56.5 % of total contribution to NHLs). In addition to the background CH4, recent emissions from Canada, the Middle East, and Europe contribute 16.9 %, 12.1 %, and 8.4 %, respectively, to the total change in the SCA in the NHLs. The remaining contributions are due to changes in emissions and transport from other regions. The three largest regional contributions are driven by increases in summer emissions from the Boreal Plains in Canada, decreases in winter emissions across Europe, and a combination of increases in summer emissions and decreases in winter emissions over the Arabian Peninsula and Caspian Sea in the Middle East. These results highlight that changes in the observed seasonal cycle can be an indicator of changing emission regimes in local and non-local regions, particularly in the NHL, where the change is counterintuitive.</p

Growth in Stratospheric Chlorine from Short-Lived Chemicals not Controlled by the Montreal Protocol

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS (ClyVSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl3), dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), trichloroethene (C2HCl3), and 1,2-dichloroethane (CH2ClCH2Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection of source gases dominates this supply, accounting for ∼83% of the total. The remainder comes from VSLS-derived organic products, phosgene (COCl2, 7%) and formyl chloride (CHClO, 2%), and also hydrogen chloride (HCl, 8%). Stratospheric ClyVSLS increased by ∼52% between 2005 and 2013, with a mean growth rate of 3.7 ppt Cl/yr. This increase is due to recent and ongoing growth in anthropogenic CH2Cl2 - the most abundant chlorinated VSLS not controlled by the Montreal Protocol. ©2015

Role of OH variability in the stalling of the global atmospheric CH4 growth rate from 1999 to 2006

The growth in atmospheric methane (CH4) concentrations over the past two decades has shown large variability on a timescale of several years. Prior to 1999 the globally averaged CH4 concentration was increasing at a rate of 6.0 ppb/yr, but during a stagnation period from 1999 to 2006 this growth rate slowed to 0.6 ppb/yr. From 2007 to 2009 the growth rate again increased to 4.9 ppb/yr. These changes in growth rate are usually ascribed to variations in CH4 emissions. We have used a 3-D global chemical transport model, driven by meteorological reanalyses and variations in global mean hydroxyl (OH) concentrations derived from CH3CCl3 observations from two independent networks, to investigate these CH4 growth variations. The model shows that between 1999 and 2006, changes in the CH4 atmospheric loss contributed significantly to the suppression in global CH4 concentrations relative to the pre-1999 trend. The largest factor in this is relatively small variations in global mean OH on a timescale of a few years, with minor contributions of atmospheric transport of CH4 to its sink region and of atmospheric temperature. Although changes in emissions may be important during the stagnation period, these results imply a smaller variation is required to explain the observed CH4 trends. The contribution of OH variations to the renewed CH4 growth after 2007 cannot be determined with data currently available

Decreasing seasonal cycle amplitude of methane in the northern high latitudes being driven by lower-latitude changes in emissions and transport

Atmospheric methane (CH4) concentrations are rising, which are expected to lead to a corresponding increase in the global seasonal cycle amplitude (SCA) – the difference between its seasonal maximum and minimum values. The reaction between CH4 and its main sink, OH, is dependent on the amount of CH4 and OH in the atmosphere. The concentration of OH varies seasonally, and due to the increasing burden of CH4 in the atmosphere, it is expected that the SCA of CH4 will increase due to the increased removal of CH4 through a reaction with OH in the atmosphere. Spatially varying changes in the SCA could indicate long-term persistent variations in the seasonal sources and sinks, but such SCA changes have not been investigated. Here we use surface flask measurements and a 3D chemical transport model (TOMCAT) to diagnose changes in the SCA of atmospheric CH4 between 1995–2020 and attribute the changes regionally to contributions from different sectors. We find that the observed SCA decreased by 4 ppb (7.6 %) in the northern high latitudes (NHLs; 60–90∘ N), while the SCA increased globally by 2.5 ppb (6.5 %) during this time period. TOMCAT reproduces the change in the SCA at observation sites across the globe. Therefore, we use it to attribute regions which are contributing to the changes in the NHL SCA, which shows an unexpected change in the SCA that differs from the rest of the world. We find that well-mixed background CH4, likely from emissions originating in, and transported from, more southerly latitudes has the largest impact on the decreasing SCA in the NHLs (56.5 % of total contribution to NHLs). In addition to the background CH4, recent emissions from Canada, the Middle East, and Europe contribute 16.9 %, 12.1 %, and 8.4 %, respectively, to the total change in the SCA in the NHLs. The remaining contributions are due to changes in emissions and transport from other regions. The three largest regional contributions are driven by increases in summer emissions from the Boreal Plains in Canada, decreases in winter emissions across Europe, and a combination of increases in summer emissions and decreases in winter emissions over the Arabian Peninsula and Caspian Sea in the Middle East. These results highlight that changes in the observed seasonal cycle can be an indicator of changing emission regimes in local and non-local regions, particularly in the NHL, where the change is counterintuitive

First validation of high-resolution satellite-derived methane emissions from an active gas leak in the UK

Atmospheric methane (CH4) is the second-most-important anthropogenic greenhouse gas and has a 20-year global warming potential 82 times greater than carbon dioxide (CO2). Anthropogenic sources account for g1/4g% of global CH4 emissions, of which 20g% come from oil and gas exploration, production and distribution. High-resolution satellite-based imaging spectrometers are becoming important tools for detecting and monitoring CH4 point source emissions, aiding mitigation. However, validation of these satellite measurements, such as those from the commercial GHGSat satellite constellation, has so far not been documented for active leaks. Here we present the monitoring and quantification, by GHGSat's satellites, of the CH4 emissions from an active gas leak from a downstream natural gas distribution pipeline near Cheltenham, UK, in the spring and summer of 2023 and provide the first validation of the satellite-derived emission estimates using surface-based mobile greenhouse gas surveys. We also use a Lagrangian transport model, the UK Met Office's Numerical Atmospheric-dispersion Modelling Environment (NAME), to estimate the flux from both satellite-and ground-based observation methods and assess the leak's contribution to observed concentrations at a local tall tower site (30gkm away). We find GHGSat's emission estimates to be in broad agreement with those made from the in situ measurements. During the study period (March-June 2023) GHGSat's emission estimates are 236-1357gkggCH4gh-1, whereas the mobile surface measurements are 634-846gkggCH4gh-1. The large variability is likely down to variations in flow through the pipe and engineering works across the 11-week period. Modelled flux estimates in NAME are 181-1243gkggCH4gh-1, which are lower than the satellite-and mobile-survey-derived fluxes but are within the uncertainty. After detecting the leak in March 2023, the local utility company was contacted, and the leak was fixed by mid-June 2023. Our results demonstrate that GHGSat's observations can produce flux estimates that broadly agree with surface-based mobile measurements. Validating the accuracy of the information provided by targeted, high-resolution satellite monitoring shows how it can play an important role in identifying emission sources, including unplanned fugitive releases that are inherently challenging to identify, track, and estimate their impact and duration. Rapid, widespread access to such data to inform local action to address fugitive emission sources across the oil and gas supply chain could play a significant role in reducing anthropogenic contributions to climate change.</p

Satellite constraint on the tropospheric ozone radiative effect

Tropospheric ozone directly affects the radiative balance of the Earth through interaction with shortwave and longwave radiation. Here we use measurements of tropospheric ozone from the Tropospheric Emission Spectrometer satellite instrument, together with chemical transport and radiative transfer models, to produce a first estimate of the stratospherically adjusted annual radiative effect (RE) of tropospheric ozone. We show that differences between modeled and observed ozone concentrations have little impact on the RE, indicating that our present-day tropospheric ozone RE estimate of 1.17 ± 0.03 W m−2 is robust. The RE normalized by column ozone decreased between the preindustrial and the present-day. Using a simulation with historical biomass burning and no anthropogenic emissions, we calculate a radiative forcing of 0.32 W m−2 for tropospheric ozone, within the current best estimate range. We propose a radiative kernel approach as an efficient and accurate tool for calculating ozone REs in simulations with similar ozone abundances