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

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

Emission factors for open and domestic biomass burning for use in atmospheric models

Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially true for non-methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New EF should improve regional to global BB emissions estimates and therefore, the input for atmospheric models. In this work we present an up-to-date, comprehensive tabulation of EF for known pyrogenic species based on measurements made in smoke that has cooled to ambient temperature, but not yet undergone significant photochemical processing. All EFs are converted to one standard form (g compound emitted per kg dry biomass burned) using the carbon mass balance method and they are categorized into 14 fuel or vegetation types. Biomass burning terminology is defined to promote consistency. We compile a large number of measurements of biomass consumption per unit area for important fire types and summarize several recent estimates of global biomass consumption by the major types of biomass burning. Post emission processes are discussed to provide a context for the emission factor concept within overall atmospheric chemistry and also highlight the potential for rapid changes relative to the scale of some models or remote sensing products. Recent work shows that individual biomass fires emit significantly more gas-phase NMOC than previously thought and that including additional NMOC can improve photochemical model performance. A detailed global estimate suggests that BB emits at least 400 Tg yr^(−1) of gas-phase NMOC, which is almost 3 times larger than most previous estimates. Selected recent results (e.g. measurements of HONO and the BB tracers HCN and CH_3CN) are highlighted and key areas requiring future research are briefly discussed

Trend in ice moistening the stratosphere – constraints from isotope data of water and methane

Water plays a major role in the chemistry and radiative budget of the stratosphere. Air enters the stratosphere predominantly in the tropics, where the very low temperatures around the tropopause constrain water vapour mixing ratios to a few parts per million. Observations of stratospheric water vapour show a large positive long-term trend, which can not be explained by change in tropopause temperatures. Trends in the partitioning between vapour and ice of water entering the stratosphere have been suggested to resolve this conundrum. We present measurements of stratospheric H_(2)O, HDO, CH_4 and CH_(3)D in the period 1991–2007 to evaluate this hypothesis. Because of fractionation processes during phase changes, the hydrogen isotopic composition of H_(2)O is a sensitive indicator of changes in the partitioning of vapour and ice. We find that the seasonal variations of H_(2)O are mirrored in the variation of the ratio of HDO to H_(2)O with a slope of the correlation consistent with water entering the stratosphere mainly as vapour. The variability in the fractionation over the entire observation period is well explained by variations in H_(2)O. The isotopic data allow concluding that the trend in ice arising from particulate water is no more than (0.01±0.13) ppmv/decade in the observation period. Our observations suggest that between 1991 and 2007 the contribution from changes in particulate water transported through the tropopause plays only a minor role in altering in the amount of water entering the stratosphere

Comment on: “The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN Field Campaign” by Hofzumahaus et al. and “Intercomparison of tropospheric OH radical measurements by multiple folded long-path laser absorption and laser induced fluorescence” by Brauers et al.

Calibration of laser induced fluorescence (LIF) instruments that measure OH is challenging because it is difficult to reliably introduce a known amount of this reactive radical into a measurement apparatus. In a recent paper, Hofzumahaus et al., [1996] describe a novel and seemingly simple technique to accomplish this goal: they dissociate trace quantities of water vapor in air with a low pressure mercury (Hg) lamp to produce low concentrations (10^5 - 10^9 cm^(-3)) of OH (R1)

Observation of isoprene hydroxynitrates in the southeastern United States and implications for the fate of NO_x

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NO_x environments. Production and loss of IN have a significant influence on the NO_x cycle and tropospheric O_3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/−3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed

OH, HO_2, NO in two biomass burning plumes: Sources of HO_x and implications for ozone production

The ER-2 made two descents through upper tropospheric biomass burning plumes during ASHOE/MAESA. HO_x (= OH + HO_2) concentrations are largely self-limited outside the plumes, but become progressively more limited by reactions with NO_x (= NO + NO_2) at the higher NO_x concentrations inside the plumes. Sources of HO_x in addition to H_(2)O and CH_4 oxidation are required to balance the known HOx sinks both in the plumes and in the background upper troposphere. HO_x concentrations were consistently underestimated by a model constrained by observed NO_x concentrations. The size of the model underestimate is reduced when acetone photolysis is included. Models which do not include the additional HO_x sources required to balance the HO_x budget are likely to underestimate ozone production rates