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The atmospheric oxidation of biogenic volatile organic compounds (BVOC) by OH radicals over tropical rainforests impacts local particle production and the lifetime of globally distributed chemically and radiatively active gases. For the pristine Amazon rainforest during the dry season, we empirically determined the diurnal OH radical variability at the forest-atmosphere interface region between 80 and 325 m from 07:00 to 15:00 LT using BVOC measurements. A dynamic time warping approach was applied showing that median averaged mixing times between 80 to 325 m decrease from 105 to 15 min over this time period. The inferred OH concentrations show evidence for an early morning OH peak (07:00–08:00 LT) and an OH maximum (14:00 LT) reaching 2.2 (0.2, 3.8) × 106 molecules cm−3 controlled by the coupling between BVOC emission fluxes, nocturnal NOx accumulation, convective turbulence, air chemistry and photolysis rates. The results were evaluated with a turbulence resolving transport (DALES), a regional scale (WRF-Chem) and a global (EMAC) atmospheric chemistry model. [ABSTRACT FROM AUTHOR]

We examine the dependence of the inferred isoprene surface emission flux from atmospheric concentration on the diurnal variability of the convective boundary layer (CBL). A series of systematic numerical experiments carried out using the mixed-layer technique enabled us to study the sensitivity of isoprene fluxes to the entrainment process, the partition of surface fluxes, the horizontal advection of warm/cold air masses and subsidence. Our findings demonstrate the key role played by the evolution of boundary layer height in modulating the retrieved isoprene flux. More specifically, inaccurate values of the potential temperature lapse rate lead to changes in the dilution capacity of the CBL and as a result the isoprene flux may be overestimated or underestimated by as much as 20%. The inferred emission flux estimated in the early morning hours is highly dependent on the accurate estimation of the discontinuity of the thermodynamic values between the residual layer and the rapidly forming CBL. Uncertainties associated with the partition of the sensible and latent heat flux also yield large deviations in the calculation of the isoprene surface flux. Similar results are obtained if we neglect the influence of warm or cold advection in the development of the CBL.We show that all the above-mentioned processes are non-linear, for which reason the dynamic and chemical evolutions of the CBL must be solved simultaneously. Based on the discussion of our results, we suggest the measurements needed to correctly apply the mixed-layer technique in order to minimize the uncertainties associated with the diurnal variability of the convective boundary layer. [ABSTRACT FROM AUTHOR]

We present an evaluation of sources, sinks and turbulent transport of nitrogen oxides, ozone and volatile organic compounds (VOC) in the boundary layer over French Guyana and Suriname during the October 2005 GABRIEL campaign by simulating observations with a single-column chemistry and climate model (SCM) along a zonal transect. Simulated concentrations of O3 and NO as well as NO2 photolysis rates over the forest agree well with observations when a small soil-biogenic NO emission flux was applied. This suggests that the photochemical conditions observed during GABRIEL reflect a pristine tropical low-NOx regime. The SCM uses a compensation point approach to simulate nocturnal deposition and daytime emissions of acetone and methanol and produces daytime boundary layer mixing ratios in reasonable agreement with observations. The area average isoprene emission flux, inferred from the observed isoprene mixing ratios and boundary layer height, is about half the flux simulated with commonly applied emission algorithms. The SCM nevertheless simulates too high isoprene mixing ratios, whereas hydroxyl concentrations are strongly underestimated compared to observations, which can at least partly explain the discrepancy. Furthermore, the model substantially overestimates the isoprene oxidation products methlyl vinyl ketone (MVK) and methacrolein (MACR) partly due to a simulated nocturnal increase due to isoprene oxidation. This increase is most prominent in the residual layer whereas in the nocturnal inversion layer we simulate a decrease in MVK and MACR mixing ratios, assuming efficient removal of MVK and MACR. Entrainment of residual layer air masses, which are enhanced in MVK and MACR and other isoprene oxidation products, into the growing boundary layer poses an additional sink for OH which is thus not available for isoprene oxidation. Based on these findings, we suggest pursuing measurements of the tropical residual layer chemistry with a focus on the nocturnal depletion of isoprene and its oxidation products. [ABSTRACT FROM AUTHOR]

We investigate the interaction between the ammonium nitrate aerosol ( N A O 3 ) abundance and convective boundary-layer (CBL) dynamics by means of a large-eddy simulation (LES) framework. In our LES model the CBL dynamics is solved coupled with radiation, chemistry, and surface exchange. Concerning the aerosol coupling we assume a simplified representation that accounts for black carbon, aerosol water and inorganic aerosols, focusing on the semi-volatile ammonium nitrate aerosol within the CBL. The aerosol absorption and scattering of shortwave radiation is also taken into consideration. We use a data set of observations taken at the Cabauw Experimental Site for Atmospheric Research during the IMPACT/EUCAARI (European Integrated Project on Aerosol, Cloud, Climate, and Air Quality Interactions) campaign to successfully evaluate our LES approach. We highlight that our LES framework reproduces the observations of the ratio between gas-phase nitrate and total nitrate at the surface, with a diurnally-averaged overestimation of only ≈12%. We show that the dependence between gas-aerosol conversion of nitrate and CBL (thermo)dynamics produces highly non-linear concentration and turbulent flux vertical profiles. The flux profiles maximize at around 1/3 of the CBL. Close to the surface, we show that the outgassing of N A O 3 affects the dry deposition of nitrate. This outgassing is responsible for the high deposition velocities obtained from the concentration and flux measurements during observational campaigns. To account for the influence of CBL (thermo)dynamics on gas-aerosol conversion we propose an effective turbulent exchange coefficient based on an analysis of the flux budget equation of aerosol nitrate calculated by our LES. The implementation of this effective turbulent exchange coefficient in a 1D model leads to a better agreement with the LES results and with surface observations. [ABSTRACT FROM AUTHOR]