Items

Advanced search

Influence of corona discharge on the ozone budget in the tropical free troposphere: a case study of deep convection during GABRIEL

Convective redistribution of ozone and its precursors between the boundary layer (BL) and the free troposphere (FT) influences photochemistry, in particular in the middle and upper troposphere (UT). We present a case study of convective transport during the GABRIEL campaign over the tropical rain forest in Suriname in October 2005. During one measurement flight the inflow and outflow regions of a cumulonimbus cloud (Cb) have been characterized. We identified a distinct layer between 9 and 11 km altitude with enhanced mixing ratios of CO, O3, HOx, acetone and acetonitrile. The elevated O3 contradicts the expectation that convective transport brings low-ozone air from the boundary layer to the outflow region. Entrainment of ozone-rich air is estimated to account for 62% (range: 33–91%) of the observed O3. Ozone is enhanced by only 5–6% by photochemical production in the outflow due to enhanced NO from lightning, based on model calculations using observations including the first reported HOx measurements over the tropical rainforest. The "excess" ozone in the outflow is most probably due to direct production by corona discharge associated with lightning. We deduce a production rate of 5.12 × 1028 molecules O3 flash−1 (range: 9.89 × 1026–9.82 × 1028 molecules O3 flash−1), which is at the upper limit of the range reported previously.
Air–sea exchange and gas–particle partitioning of polycyclic aromatic hydrocarbons in the Mediterranean

Polycyclic aromatic hydrocarbon (PAH) concentration in air of the central and eastern Mediterranean in summer 2010 was 1.45 (0.30–3.25) ng m−3 (sum of 25 PAHs), with 8 (1–17)% in the particulate phase, almost exclusively associated with particles < 0.25 μm. The total deposition flux of particulate PAHs was 0.3–0.5 μ g m−2 yr−1. The diffusive air–sea exchange fluxes of fluoranthene and pyrene were mostly found net-depositional or close to phase equilibrium, while retene was net-volatilisational in a large sea region. Regional fire activity records in combination with box model simulations suggest that seasonal depositional input of retene from biomass burning into the surface waters during summer is followed by an annual reversal of air–sea exchange, while interannual variability is dominated by the variability of the fire season. One-third of primary retene sources to the sea region in the period 2005–2010 returned to the atmosphere as secondary emissions from surface seawaters. It is concluded that future negative emission trends or interannual variability of regional sources may trigger the sea to become a secondary PAH source through reversal of diffusive air–sea exchange. Capsule: In late summer the seawater surface in the Mediterranean has turned into a temporary secondary source of PAH, obviously related to biomass burning in the region.
Assessment of uncertainties of an aircraft-based mass balance approach for quantifying urban greenhouse gas emissions

Urban environments are the primary contributors to global anthropogenic carbon emissions. Because much of the growth in CO2 emissions will originate from cities, there is a need to develop, assess, and improve measurement and modeling strategies for quantifying and monitoring greenhouse gas emissions from large urban centers. In this study the uncertainties in an aircraft-based mass balance approach for quantifying carbon dioxide and methane emissions from an urban environment, focusing on Indianapolis, IN, USA, are described. The relatively level terrain of Indianapolis facilitated the application of mean wind fields in the mass balance approach. We investigate the uncertainties in our aircraft-based mass balance approach by (1) assessing the sensitivity of the measured flux to important measurement and analysis parameters including wind speed, background CO2 and CH4, boundary layer depth, and interpolation technique, and (2) determining the flux at two or more downwind distances from a point or area source (with relatively large source strengths such as solid waste facilities and a power generating station) in rapid succession, assuming that the emission flux is constant. When we quantify the precision in the approach by comparing the estimated emissions derived from measurements at two or more downwind distances from an area or point source, we find that the minimum and maximum repeatability were 12 and 52%, with an average of 31%. We suggest that improvements in the experimental design can be achieved by careful determination of the background concentration, monitoring the evolution of the boundary layer through the measurement period, and increasing the number of downwind horizontal transect measurements at multiple altitudes within the boundary layer.
The contribution of fungal spores and bacteria to regional and global aerosol number and ice nucleation immersion freezing rates

Primary biological aerosol particles (PBAPs) may play an important role in aerosol–climate interactions, in particular by affecting ice formation in mixed phase clouds. However, the role of PBAPs is poorly understood because the sources and distribution of PBAPs in the atmosphere are not well quantified. Here we include emissions of fungal spores and bacteria in a global aerosol microphysics model and explore their contribution to concentrations of supermicron particle number, cloud condensation nuclei (CCN) and immersion freezing rates. Simulated surface annual mean concentrations of fungal spores are ~ 2.5 × 104 m−3 over continental midlatitudes and 1 × 105 m−3 over tropical forests. Simulated surface concentrations of bacteria are 2.5 × 104 m−3 over most continental regions and 5 × 104 m−3 over grasslands of central Asia and North America. These simulated surface number concentrations of fungal spores and bacteria are broadly in agreement with the limited available observations. We find that fungal spores and bacteria contribute 8 and 5% respectively to simulated continental surface mean supermicron number concentrations, but have very limited impact on CCN concentrations, altering regional concentrations by less than 1%. In agreement with previous global modelling studies, we find that fungal spores and bacteria contribute very little (3 × 10−3%, even when we assume upper limits for ice nucleation activity) to global average immersion freezing ice nucleation rates, which are dominated by soot and dust. However, at lower altitudes (400 to 600 hPa), where warmer temperatures mean that soot and dust may not nucleate ice, we find that PBAP controls the immersion freezing ice nucleation rate. This demonstrates that PBAPs can be of regional importance for IN formation, in agreement with case study observations.
Constraining terrestrial ecosystem CO2 fluxes by integrating models of biogeochemistry and atmospheric transport and data of surface carbon fluxes and atmospheric CO2 concentrations

Regional net carbon fluxes of terrestrial ecosystems could be estimated with either biogeochemistry models by assimilating surface carbon flux measurements or atmospheric CO2 inversions by assimilating observations of atmospheric CO2 concentrations. Here we combine the ecosystem biogeochemistry modeling and atmospheric CO2 inverse modeling to investigate the magnitude and spatial distribution of the terrestrial ecosystem CO2 sources and sinks. First, we constrain a terrestrial ecosystem model (TEM) at site level by assimilating the observed net ecosystem production (NEP) for various plant functional types. We find that the uncertainties of model parameters are reduced up to 90% and model predictability is greatly improved for all the plant functional types (coefficients of determination are enhanced up to 0.73). We then extrapolate the model to a global scale at a 0.5° × 0.5° resolution to estimate the large-scale terrestrial ecosystem CO2 fluxes, which serve as prior for atmospheric CO2 inversion. Second, we constrain the large-scale terrestrial CO2 fluxes by assimilating the GLOBALVIEW-CO2 and mid-tropospheric CO2 retrievals from the Atmospheric Infrared Sounder (AIRS) into an atmospheric transport model (GEOS-Chem). The transport inversion estimates that: (1) the annual terrestrial ecosystem carbon sink in 2003 is −2.47 Pg C yr−1, which agrees reasonably well with the most recent inter-comparison studies of CO2 inversions (−2.82 Pg C yr−1); (2) North America temperate, Europe and Eurasia temperate regions act as major terrestrial carbon sinks; and (3) The posterior transport model is able to reasonably reproduce the atmospheric CO2 concentrations, which are validated against Comprehensive Observation Network for TRace gases by AIrLiner (CONTRAIL) CO2 concentration data. This study indicates that biogeochemistry modeling or atmospheric transport and inverse modeling alone might not be able to well quantify regional terrestrial carbon fluxes. However, combining the two modeling approaches and assimilating data of surface carbon flux as well as atmospheric CO2 mixing ratios might significantly improve the quantification of terrestrial carbon fluxes.
Countergradient heat flux observations during the evening transition period

Gradient-based turbulence models generally assume that the buoyancy flux ceases to introduce heat into the surface layer of the atmospheric boundary layer in temporal consonance with the gradient of the local virtual potential temperature. Here, we hypothesize that during the evening transition a delay exists between the instant when the buoyancy flux goes to zero and the time when the local gradient of the virtual potential temperature indicates a sign change. This phenomenon is studied using a range of data collected over several intensive observational periods (IOPs) during the Boundary Layer Late Afternoon and Sunset Turbulence field campaign conducted in Lannemezan, France. The focus is mainly on the lower part of the surface layer using a tower instrumented with high-speed temperature and velocity sensors. The results from this work confirm and quantify a flux-gradient delay. Specifically, the observed values of the delay are ~ 30–80 min. The existence of the delay and its duration can be explained by considering the convective timescale and the competition of forces associated with the classical Rayleigh–Bénard problem. This combined theory predicts that the last eddy formed while the sensible heat flux changes sign during the evening transition should produce a delay. It appears that this last eddy is decelerated through the action of turbulent momentum and thermal diffusivities, and that the delay is related to the convective turnover timescale. Observations indicate that as horizontal shear becomes more important, the delay time apparently increases to values greater than the convective turnover timescale.
Comprehensive assessment of meteorological conditions and airflow connectivity during HCCT-2010

This study presents a comprehensive assessment of the meteorological conditions and atmospheric flow during the Lagrangian-type "Hill Cap Cloud Thuringia 2010" experiment (HCCT-2010), which was performed in September and October 2010 at Mt. Schmücke in the Thuringian Forest, Germany and which used observations at three measurement sites (upwind, in-cloud, and downwind) to study physical and chemical aerosol–cloud interactions. A Lagrangian-type hill cap cloud experiment requires not only suitable cloud conditions but also connected airflow conditions (i.e. representative air masses at the different measurement sites). The primary goal of the present study was to identify time periods during the 6-week duration of the experiment in which these conditions were fulfilled and therefore which are suitable for use in further data examinations. The following topics were studied in detail: (i) the general synoptic weather situations, including the mesoscale flow conditions, (ii) local meteorological conditions and (iii) local flow conditions. The latter were investigated by means of statistical analyses using best-available quasi-inert tracers, SF6 tracer experiments in the experiment area, and regional modelling. This study represents the first application of comprehensive analyses using statistical measures such as the coefficient of divergence (COD) and the cross-correlation in the context of a Lagrangian-type hill cap cloud experiment. This comprehensive examination of local flow connectivity yielded a total of 14 full-cloud events (FCEs), which are defined as periods during which all connected flow and cloud criteria for a suitable Lagrangian-type experiment were fulfilled, and 15 non-cloud events (NCEs), which are defined as periods with connected flow but no cloud at the summit site, and which can be used as reference cases. The overall evaluation of the identified FCEs provides the basis for subsequent investigations of the measured chemical and physical data during HCCT-2010 (see <a href="https://www.atmos-chem-phys.net/special_issue287.html"target="_blank">https://www.atmos-chem-phys.net/special_issue287.html</a>). Results obtained from the statistical flow analyses and regional-scale modelling performed in this study indicate the existence of a strong link between the three measurement sites during the FCEs and NCEs, particularly under conditions of constant southwesterly flow, high wind speeds and slightly stable stratification. COD analyses performed using continuous measurements of ozone and particle (49 nm diameter size bin) concentrations at the three sites revealed, particularly for COD values < 0.1, very consistent time series (i.e. close links between air masses at the different sites). The regional-scale model simulations provided support for the findings of the other flow condition analyses. Cross-correlation analyses revealed typical overflow times of ~15–30 min between the upwind and downwind valley sites under connected flow conditions. The results described here, together with those obtained from the SF6 tracer experiments performed during the experiment, clearly demonstrate that (a) under appropriate meteorological conditions a Lagrangian-type approach is valid and (b) the connected flow validation procedure developed in this work is suitable for identifying such conditions. Overall, it is anticipated that the methods and tools developed and applied in the present study will prove useful in the identification of suitable meteorological and connected airflow conditions during future Lagrangian-type hill cap cloud experiments.
Corrigendum to "Microphysical Process Rates and Global Aerosol-Cloud Interactions" published in Atmos. Chem. Phys., 13, 9855–9867, 2013

A mistake swapped process rates between autoconversion and accretion in global model solutions. Revised figures are presented. The accretion to autoconversion ratio in the model does increase with Liquid Water Path (LWP) as in the steady state model but biases remain. Simulated autoconversion rates are too high. Adjusting process rates following the steady state model ideas leads to an improvement in process rates. The main conclusion is unaffected.
Uptake and emission of VOCs near ground level below a mixed forest at Borden, Ontario

Understanding of the atmosphere/forest canopy exchange of volatile organic compounds (VOCs) requires insight into the deposition, emission, and chemical reactions of VOCs below the canopy. Between 18 July and 9 August 2009, VOCs were measured with proton-transfer-reaction mass spectrometry (PTR-MS) at six heights between 1 and 6 m beneath a 23 m high mixed-forest canopy. Measured VOCs included methanol, isoprene, acetone, methacrolein and methyl vinyl ketone (MACR + MVK), monoterpenes, and sesquiterpenes. There are pronounced differences in the behaviour of isoprene and its by-products and that of the terpenes. Non-terpene mixing ratios increase with height, suggesting predominantly downward fluxes. In contrast, the terpene mixing ratios decrease with height, suggesting upward fluxes. A 1-D canopy model was used to compare results to measurements with and without surface deposition of isoprene and MACR + MVK and emissions of monoterpenes and sesquiterpenes. Results suggest deposition velocities of 2.7 mm s−1 for isoprene and 1.2 mm s−1 for MACR + MVK and daytime surface emission rates of 63 μg m−2 h−1 for monoterpenes. The modelled isoprene surface deposition is approximately 2% of the canopy-top isoprene emissions and the modelled emissions of monoterpenes comprise approximately 15 to 27% of the canopy-top monoterpene emissions to the atmosphere. These results suggest that surface monoterpene emissions are significant for forest canopy/atmosphere exchange for this mixed-forest location and surface uptake is relatively small for all the species measured in this study.
Improvement and further development in CESM/CAM5: gas-phase chemistry and inorganic aerosol treatments

Gas-phase chemistry and subsequent gas-to-particle conversion processes such as new particle formation, condensation, and thermodynamic partitioning have large impacts on air quality, climate, and public health through influencing the amounts and distributions of gaseous precursors and secondary aerosols. Their roles in global air quality and climate are examined in this work using the Community Earth System Model version 1.0.5 (CESM1.0.5) with the Community Atmosphere Model version 5.1 (CAM5.1) (referred to as CESM1.0.5/CAM5.1). CAM5.1 includes a simple chemistry that is coupled with a 7-mode prognostic Modal Aerosol Model (MAM7). MAM7 includes classical homogenous nucleation (binary and ternary) and activation nucleation (empirical first-order power law) parameterizations, and a highly simplified inorganic aerosol thermodynamics treatment that only simulates particulate-phase sulfate and ammonium. In this work, a new gas-phase chemistry mechanism based on the 2005 Carbon Bond Mechanism for Global Extension (CB05_GE) and several advanced inorganic aerosol treatments for condensation of volatile species, ion-mediated nucleation (IMN), and explicit inorganic aerosol thermodynamics for sulfate, ammonium, nitrate, sodium, and chloride have been incorporated into CESM/CAM5.1-MAM7. Compared to the simple gas-phase chemistry, CB05_GE can predict many more gaseous species, and thus could improve model performance for PM2.5, PM10, PM components, and some PM gaseous precursors such as SO2 and NH3 in several regions as well as aerosol optical depth (AOD) and cloud properties (e.g., cloud fraction (CF), cloud droplet number concentration (CDNC), and shortwave cloud forcing, SWCF) on the global scale. The modified condensation and aqueous-phase chemistry could further improve the prediction of additional variables such as HNO3, NO2, and O3 in some regions, and new particle formation rate (J) and AOD on the global scale. IMN can improve the prediction of secondary PM2.5 components, PM2.5, and PM10 over Europe as well as AOD and CDNC on the global scale. The explicit inorganic aerosol thermodynamics using the ISORROPIA II model improves the prediction of all major PM2.5 components and their gaseous precursors in some regions as well as downwelling shortwave radiation, SWCF, and cloud condensation nuclei at a supersaturation of 0.5% on the global scale. For simulations of 2001–2005 with all the modified and new treatments, the improved model predicts that on global average, SWCF increases by 2.7 W m−2, reducing the normalized mean bias (NMB) of SWCF from −5.4 to 1.2%. Uncertainties in emissions can largely explain the inaccurate prediction of precursor gases (e.g., SO2, NH3, and NO) and primary aerosols (e.g., black carbon and primary organic matter). Additional factors leading to the discrepancies between model predictions and observations include assumptions associated with equilibrium partitioning for fine particles assumed in ISORROPIA II, irreversible gas/particle mass transfer treatment for coarse particles, uncertainties in model treatments such as dust emissions, secondary organic aerosol formation, multi-phase chemistry, cloud microphysics, aerosol–cloud interaction, dry and wet deposition, and model parameters (e.g., accommodation coefficients and prefactors of the nucleation power law) as well as uncertainties in model configuration such as the use of a coarse-grid resolution.