Global CO_2 fluxes inferred from surface air-sample measurements and from TCCON retrievals of the CO_2 total column

We present the first estimate of the global distribution of CO_2 surface fluxes from 14 stations of the Total Carbon Column Observing Network (TCCON). The evaluation of this inversion is based on 1) comparison with the fluxes from a classical inversion of surface air-sample-measurements, and 2) comparison of CO_2 mixing ratios calculated from the inverted fluxes with independent aircraft measurements made during the two years analyzed here, 2009 and 2010. The former test shows similar seasonal cycles in the northern hemisphere and consistent regional carbon budgets between inversions from the two datasets, even though the TCCON inversion appears to be less precise than the classical inversion. The latter test confirms that the TCCON inversion has improved the quality (i.e., reduced the uncertainty) of the surface fluxes compared to the assumed or prior fluxes. The consistency between the surface-air-sample-based and the TCCON-based inversions despite remaining flaws in transport models opens the possibility of increased accuracy and robustness of flux inversions based on the combination of both data sources and confirms the usefulness of space-borne monitoring of the CO_2 column

Sources of variations in total column carbon dioxide

Observations of gradients in the total CO_2 column, (CO2), are expected to provide improved constraints on surface fluxes of CO_2. Here we use a general circulation model with a variety of prescribed carbon fluxes to investigate how variations in (CO_2) arise. On diurnal scales, variations are small and are forced by both local fluxes and advection. On seasonal scales, gradients are set by the north-south flux distribution. On synoptic scales, variations arise due to large-scale eddy-driven disturbances of the meridional gradient. In this case, because variations in (CO_2) are tied to synoptic activity, significant correlations exist between (CO_2) and dynamical tracers. We illustrate how such correlations can be used to describe the north-south gradients of (CO_2) and the underlying fluxes on continental scales. These simulations suggest a novel analysis framework for using column observations in carbon cycle science

Impact of the isoprene photochemical cascade on tropical ozone

Tropical tropospheric ozone affects Earth's radiative forcing and the oxidative capacity of the atmosphere. Considerable work has been devoted to the study of the processes controlling its budget. Yet, large discrepancies between simulated and observed tropical tropospheric ozone remain. Here, we characterize some of the mechanisms by which the photochemistry of isoprene impacts the budget of tropical ozone. At the regional scale, we use forward sensitivity simulation to explore the sensitivity to the representation of isoprene nitrates. We find that isoprene nitrates can account for up to 70% of the local NO_x = NO+NO_2 sink. The resulting modulation of ozone can be well characterized by their net modulation of NO_x. We use adjoint sensitivity simulations to demonstrate that the oxidation of isoprene can affect ozone outside of continental regions through the transport of NO_x over near-shore regions (e.g., South Atlantic) and the oxidation of isoprene outside of the boundary layer far from its emissions regions. The latter mechanism is promoted by the simulated low boundary-layer oxidative conditions. In our simulation, ~20% of the isoprene is oxidized above the boundary layer in the tropics. Changes in the interplay between regional and global effect are discussed in light of the forecasted increase in anthropogenic emissions in tropical regions

The impact of anticipation in dynamical systems

Collective motion in biology is often modelled as a dynamical system, in which individuals are represented as particles whose interactions are determined by the current state of the system. Many animals, however, including humans, have predictive capabilities, and presumably base their behavioural decisions---at least partially---upon an anticipated state of their environment. We explore a minimal version of this idea in the context of particles that interact according to a pairwise potential. Anticipation enters the picture by calculating the interparticle forces from linear extrapolations of the particle positions some time $\tau$ into the future. Simulations show that for intermediate values of $\tau$, compared to a transient time scale defined by the potential and the initial conditions, the particles form rotating clusters in which the particles are arranged in a hexagonal pattern. Analysis of the system shows that anticipation induces energy dissipation and we show that the kinetic energy asymptotically decays as $1/t$. Furthermore, we show that the angular momentum is not necessarily conserved for $\tau >0$, and that asymmetries in the initial condition therefore can cause rotational movement. These results suggest that anticipation could play an important role in collective behaviour, since it induces pattern formation and stabilises the dynamics of the system.Comment: Major revision compared to previous version. All figures replaced. Only introduction and discussion remain intac

Chemical depletion of Arctic ozone in winter 1999/2000

During Arctic winters with a cold, stable stratospheric circulation, reactions on the surface of polar stratospheric clouds (PSCs) lead to elevated abundances of chlorine monoxide (ClO) that, in the presence of sunlight, destroy ozone. Here we show that PSCs were more widespread during the 1999/2000 Arctic winter than for any other Arctic winter in the past two decades. We have used three fundamentally different approaches to derive the degree of chemical ozone loss from ozonesonde, balloon, aircraft, and satellite instruments. We show that the ozone losses derived from these different instruments and approaches agree very well, resulting in a high level of confidence in the results. Chemical processes led to a 70% reduction of ozone for a region ∼1 km thick of the lower stratosphere, the largest degree of local loss ever reported for the Arctic. The Match analysis of ozonesonde data shows that the accumulated chemical loss of ozone inside the Arctic vortex totaled 117 ± 14 Dobson units (DU) by the end of winter. This loss, combined with dynamical redistribution of air parcels, resulted in a 88 ± 13 DU reduction in total column ozone compared to the amount that would have been present in the absence of any chemical loss. The chemical loss of ozone throughout the winter was nearly balanced by dynamical resupply of ozone to the vortex, resulting in a relatively constant value of total ozone of 340 ± 50 DU between early January and late March. This observation of nearly constant total ozone in the Arctic vortex is in contrast to the increase of total column ozone between January and March that is observed during most years

Near-UV photolysis cross sections of CH_3OOH and HOCH_2OOH determined via action spectroscopy

Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10−23 cm2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections

Nitrogen oxides and PAN in plumes from boreal fires during ARCTAS-B and their impact on ozone: an integrated analysis of aircraft and satellite observations

We determine enhancement ratios for NO_x, PAN, and other NO_y species from boreal biomass burning using aircraft data obtained during the ARCTAS-B campaign and examine the impact of these emissions on tropospheric ozone in the Arctic. We find an initial emission factor for NO_x of 1.06 g NO per kg dry matter (DM) burned, much lower than previous observations of boreal plumes, and also one third the value recommended for extratropical fires. Our analysis provides the first observational confirmation of rapid PAN formation in a boreal smoke plume, with 40% of the initial NO_x emissions being converted to PAN in the first few hours after emission. We find little clear evidence for ozone formation in the boreal smoke plumes during ARCTAS-B in either aircraft or satellite observations, or in model simulations. Only a third of the smoke plumes observed by the NASA DC8 showed a correlation between ozone and CO, and ozone was depleted in the plumes as often as it was enhanced. Special observations from the Tropospheric Emission Spectrometer (TES) also show little evidence for enhanced ozone in boreal smoke plumes between 15 June and 15 July 2008. Of the 22 plumes observed by TES, only 4 showed ozone increasing within the smoke plumes, and even in those cases it was unclear that the increase was caused by fire emissions. Using the GEOS-Chem atmospheric chemistry model, we show that boreal fires during ARCTAS-B had little impact on the median ozone profile measured over Canada, and had little impact on ozone within the smoke plumes observed by TES

Exploring Oxidation in the Remote Free Troposphere: Insights from Atmospheric Tomography (ATom)

Earth's atmosphere oxidizes the greenhouse gas methane and other gases, thus determining their lifetimes and oxidation products. Much of this oxidation occurs in the remote, relatively clean free troposphere above the planetary boundary layer, where the oxidation chemistry is thought to be much simpler and better understood than it is in urban regions or forests. The NASA airborne Atmospheric Tomography study (ATom) was designed to produce cross sections of the detailed atmospheric composition in the remote atmosphere over the Pacific and Atlantic Oceans during four seasons. As part of the extensive ATom data set, measurements of the atmosphere's primary oxidant, hydroxyl (OH), and hydroperoxyl (HO₂) are compared to a photochemical box model to test the oxidation chemistry. Generally, observed and modeled median OH and HO₂ agree to with combined uncertainties at the 2σ confidence level, which is ~±40%. For some seasons, this agreement is within ~±20% below 6 km altitude. While this test finds no significant differences, OH observations increasingly exceeded modeled values at altitudes above 8 km, becoming ~35% greater, which is near the combined uncertainties. Measurement uncertainty and possible unknown measurement errors complicate tests for unknown chemistry or incorrect reaction rate coefficients that would substantially affect the OH and HO₂ abundances. Future analysis of detailed comparisons may yield additional discrepancies that are masked in the median values