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Modelling the budget of middle atmospheric water vapour isotopes

A one-dimensional chemistry model is applied to study the stable hydrogen (D) and stable oxygen isotope (17O, 18O) composition of water vapour in stratosphere and mesosphere. In the troposphere, this isotope composition is determined by "physical' fractionation effects, that are phase changes (e.g. during cloud formation), diffusion processes (e.g. during evaporation from the ocean), and mixing of air masses. Due to these processes water vapour entering the stratosphere first shows isotope depletions in D/H relative to ocean water, which are ~5 times of those in 18O/16O, and secondly is mass-dependently fractionated (MDF), i.e. changes in the isotope ratio 17O/16O are ~0.52 times of those of 18O/16O. In contrast, in the stratosphere and mesosphere "chemical' fractionation mechanisms, that are the production of HO due to the oxidation of methane, re-cycling of H2O via the HOx family, and isotope exchange reactions considerably enhance the isotope ratios in the water vapour imported from the troposphere. The model reasonably predicts overall enhancements of the stable isotope ratios in H2O by up to ~25% for D/H, ~8.5% for 17O/16O, and ~14% for 18O/16O in the mesosphere relative to the tropopause values. The 17O/16O and 18O/16O ratios in H2O are shown to be a measure of the relative fractions of HOx that receive the O atom either from the reservoirs O2 or O3. Throughout the middle atmosphere, MDF O2 is the major donator of oxygen atoms incorporated in OH and HO2 and thus in H2O. In the stratosphere the known mass-independent fractionation (MIF) signal in O3 is in a first step transferred to the NOx family and only in a second step to HOx and H2O. In contrast to CO2, O(1D) only plays a minor role in this MIF transfer. The major uncertainty in our calculation arises from poorly quantified isotope exchange reaction rate coefficients and kinetic isotope fractionation factors.
Impact of climate variability and land use changes on global biogenic volatile organic compound emissions

A biogenic emissions scheme has been incorporated in the global dynamic vegetation model ORCHIDEE (Organizing Carbon and Hydrology in Dynamic EcosystEms) in order to calculate global biogenic emissions of isoprene, monoterpenes, methanol, acetone, acetaldehyde, formaldehyde and formic and acetic acids. Important parameters such as the leaf area index are fully determined by the global vegetation model and the influences of light extinction (for isoprene emissions) and leaf age (for isoprene and methanol emissions) are also taken into account. We study the interannual variability of biogenic emissions using the satellite-based climate forcing ISLSCP-II as well as relevant CO2 atmospheric levels, for the 1983–1995 period. Mean global emissions of 460 TgC/yr for isoprene, 117 TgC/yr for monoterpenes, 106 TgC/yr for methanol and 42 TgC/yr for acetone are predicted. The mean global emission of all biogenic compounds is 752±16 TgC/yr with extremes ranging from 717 TgC/yr in 1986 to 778 TgC/yr in 1995, that is a 8.5% increase between both. This variability differs significantly from one region to another and among the regions studied, biogenic emissions anomalies were the most variable in Europe and the least variable in Indonesia (isoprene and monoterpenes) and North America (methanol). Two scenarios of land use changes are considered using the 1983 climate and atmospheric CO2 conditions, to study the sensitivity of biogenic emissions to vegetation alteration, namely tropical deforestation and European afforestation. Global biogenic emissions are highly affected by tropical deforestation, with a 29% decrease in isoprene emission and a 22% increase in methanol emission. Global emissions are not significantly affected by European afforestation, but on a European scale, total biogenic VOCs emissions increase by 54%.
Effects of column density on I2 spectroscopy and a determination of I2 absorption cross section at 500 nm

The use of ro-vibronic spectra of I2 in the region of 543 nm to 578 nm as reference spectra for atmospheric Differential Optical Absorption Spectroscopy is studied. It is shown that the retrieval of atmospheric column densities with Differential Optical Absorption Spectroscopy set-ups at FWHM at and above 1 nm depends critically on the column density, under which the used reference spectrum was recorded. Systematic overestimation of the comparatively low atmospheric column density of I2 of the order of 13% is possible. Under low pressure conditions relevant in laboratory studies, the systematic deviations may grow up to 45%. To avoid such effects with respect to field measurements, new reference spectra of I2 were determined under column density of the order of 1016 cm-2 close to that expected for an atmospheric measurement. Two typical configurations of Differential Optical Absorption Spectroscopy, which use grating spectrometers, were chosen for the spectroscopic set-up. One spectrum was recorded at similar resolution (0.25 nm FWHM) but finer binning (0.035 nm/pixel) than previously published data. For the other (0.59 nm FWHM, 0.154 nm/pixel) no previously published spectra exist. Wavelength calibration is accurate to ±0.04 nm and ±0.11 nm respectively. The absorption cross section for the recordings was determined under low column density with an accuracy of ±4% and ±3% respectively. The absolute absorption cross section of I2 at 500 nm (wavelength: in standard air) in the continuum absorption region was determined using a method independent of iodine vapour pressure. Obtained was σI2 (500 nm)=(2.186±0.021·10-18 cm2 in very good agreement with previously published results, but at 50% smaller uncertainty. From this and previously published results a weighted average of σI2(500 nm)=(2.191±0.02)·10-18 cm2 is determined.
Rapid ventilation of the Mexico City basin and regional fate of the urban plume

Urban areas can be large emitters of air pollutants leading to negative health effects and environmental degradation. The rate of venting of these airsheds determines the pollutant loading for given emission levels, and also determines the regional impacts of the urban plume. Mexico City has approximately 20 million people living in a high altitude basin with air pollutant concentrations above the health limits most days of the year. A mesoscale meteorological model (MM5) and a particle trajectory model (FLEXPART) are used to simulate air flow within the Mexico City basin and the fate of the urban plume during the MCMA-2003 field campaign. The simulated trajectories are validated against pilot balloon and radiosonde trajectories. The residence time of air within the basin and the impacted areas are identified by episode type. Three specific cases are analysed to identify the meteorological processes involved. For most days, residence times in the basin are less than 12 h with little carry-over from day to day and little recirculation of air back into the basin. Very efficient vertical mixing leads to a vertically diluted plume which, in April, is transported predominantly towards the Gulf of Mexico. Regional accumulation was found to take place for some days however, with urban emissions sometimes staying over Mexico for more than 6 days. Knowledge of the residence times, recirculation patterns and venting mechanisms will be useful in guiding policies for improving the air quality of the MCMA.
Interactive chemistry in the Laboratoire de Météorologie Dynamique general circulation model: model description and impact analysis of biogenic hydrocarbons on tropospheric chemistry

We present a description and evaluation of LMDz-INCA, a global three-dimensional chemistry-climate model, pertaining to its recently developed NMHC version. In this substantially extended version of the model a comprehensive representation of the photochemistry of non-methane hydrocarbons (NMHC) and volatile organic compounds (VOC) from biogenic, anthropogenic, and biomass-burning sources has been included. The tropospheric annual mean methane (9.2 years) and methylchloroform (5.5 years) chemical lifetimes are well within the range of previous modelling studies and are in excellent agreement with estimates established by means of global observations. The model provides a reasonable simulation of the horizontal and vertical distribution and seasonal cycle of CO and key non-methane VOC, such as acetone, methanol, and formaldehyde as compared to observational data from several ground stations and aircraft campaigns. LMDz-INCA in the NMHC version reproduces tropospheric ozone concentrations fairly well throughout most of the troposphere. The model is applied in several sensitivity studies of the biosphere-atmosphere photochemical feedback. The impact of surface emissions of isoprene, acetone, and methanol is studied. These experiments show a substantial impact of isoprene on tropospheric ozone and carbon monoxide concentrations revealing an increase in surface O3 and CO levels of up to 30 ppbv and 60 ppbv, respectively. Isoprene also appears to significantly impact the global OH distribution resulting in a decrease of the global mean tropospheric OH concentration by approximately 0.7×105 molecules cm-3 or roughly 8% and an increase in the global mean tropospheric methane lifetime by approximately seven months. A global mean ozone net radiative forcing due to the isoprene induced increase in the tropospheric ozone burden of 0.09 W m-2 is found. The key role of isoprene photooxidation in the global tropospheric redistribution of NOx is demonstrated. LMDz-INCA calculates an increase of PAN surface mixing ratios ranging from 75 to 750 pptv and 10 to 250 pptv during northern hemispheric summer and winter, respectively. Acetone and methanol are found to play a significant role in the upper troposphere/lower stratosphere (UT/LS) budget of peroxy radicals. Calculations with LMDz-INCA show an increase in HOx concentrations region of 8 to 15% and 10 to 15% due to methanol and acetone biogenic surface emissions, respectively. The model has been used to estimate the global tropospheric CO budget. A global CO source of 3019 Tg CO yr-1 is estimated. This source divides into a primary source of 1533 Tg CO yr-1 and secondary source of 1489 Tg CO yr-1 deriving from VOC photooxidation. Global VOC-to-CO conversion efficiencies of 90% for methane and between 20 and 45% for individual VOC are calculated by LMDz-INCA.
Aerosol and NOx emission factors and submicron particle number size distributions in two road tunnels with different traffic regimes

Measurements of aerosol particle number size distributions (18–700 nm), mass concentrations (PM2.5 and PM10) and NOx were performed in the Plabutsch tunnel, Austria, and in the Kingsway tunnel, United Kingdom. These two tunnels show different characteristics regarding the roadway gradient, the composition of the vehicle fleet and the traffic frequency. The submicron particle size distributions contained a soot mode in the diameter range D=80–100 nm and a nucleation mode in the range of D=20–40 nm. In the Kingsway tunnel with a significantly lower particle number and volume concentration level than in the Plabutsch tunnel, a clear diurnal variation of nucleation and soot mode particles correlated to the traffic density was observed. In the Plabutsch tunnel, soot mode particles also revealed a diurnal variation, whereas no substantial variation was found for the nucleation mode particles. During the night a higher number concentration of nucleation mode particles were measured than soot mode particles and vice versa during the day. In this tunnel with very high soot emissions during daytime due to the heavy-duty vehicle (HDV) share of 18% and another 40% of diesel driven light-duty vehicles (LDV) semivolatile species condense on the pre-existing soot surface area rather than forming new particles by homogeneous nucleation. With the low concentration of soot mode particles in the Kingsway tunnel, also the nucleation mode particles exhibit a diurnal variation. From the measured parameters real-world traffic emission factors were estimated for the whole vehicle fleet as well as differentiated into the two categories LDV and HDV. In the particle size range D=18–700 nm, each vehicle of the mixed fleet emits (1.50±0.08)×1014 particles km-1 (Plabutsch) and (1.26±0.10)×1014 particles km-1 (Kingsway), while particle volume emission factors of 0.209±0.008 cm3 km-1 and 0.036±0.004 cm3 km-1, respectively, were obtained. PM1 emission factors of 104±4 mg km-1 (Plabutsch) and 41±4 mg km-1 (Kingsway) were calculated. Emission factors determined in this work were in good agreement with results from other studies.
Stratosphere-troposphere exchange in a summertime extratropical low: analysis

Ozone and carbon monoxide measurements sampled during two commercial flights in airstreams of a summertime midlatitude cyclone are analysed with a Lagrangian-based study (backward trajectories and a Reverse Domain Filling technique) to gain a comprehensive understanding of transport effects on trace gas distributions. The study demonstrates that summertime cyclones can be associated with deep stratosphere-troposphere transport. A tropopause fold is sampled twice in its life cycle, once in the lower troposphere (O3≃100 ppbv; CO≃90 ppbv) in the dry airstream of the cyclone, and again in the upper troposphere (O3≃200 ppbv; CO≃90 ppbv) on the northern side of the large scale potential vorticity feature associated with baroclinic development. In agreement with the maritime development of the cyclone, the chemical composition of the anticyclonic portion of the warm conveyor belt outflow (O3≃40 ppbv; CO≃85 ppbv) corresponds to the lowest mixing ratios of both ozone and carbon monoxide in the upper tropospheric airborne observations. The uncertain degree of confidence of the Lagrangian-based technique applied to a 100 km segment of upper level airborne observations with high ozone (200 ppbv) and relatively low CO (80 ppbv) observed northwest of the cyclone prevents identification of the ozone enrichment process of air parcels embedded in the cyclonic part of the upper level outflow of the warm conveyor belt. Different hypotheses of stratosphere-troposphere exchange are discussed.
Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds

A series of experiments has been conducted in the Caltech indoor smog chamber facility to investigate the water uptake properties of aerosol formed by oxidation of various organic precursors. Secondary organic aerosol (SOA) from simple and substituted cycloalkenes (C5-C8) is produced in dark ozonolysis experiments in a dry chamber (RH~5%). Biogenic SOA from monoterpenes, sesquiterpenes, and oxygenated terpenes is formed by photooxidation in a humid chamber (~50% RH). Using the hygroscopicity tandem differential mobility analyzer (HTDMA), we measure the diameter-based hygroscopic growth factor (GF) of the SOA as a function of time and relative humidity. All SOA studied is found to be slightly hygroscopic, with smaller water uptake than that of typical inorganic aerosol substances. The aerosol water uptake increases with time early in the experiments for the cycloalkene SOA, but decreases with time for the sesquiterpene SOA. This behavior could indicate competing effects between the formation of more highly oxidized polar compounds (more hygroscopic), and formation of longer-chained oligomers (less hygroscopic). All SOA also exhibit a smooth water uptake with RH with no deliquescence or efflorescence. The water uptake curves are found to be fitted well with an empirical three-parameter functional form. The measured pure organic GF values at 85% RH are between 1.09–1.16 for SOA from ozonolysis of cycloalkenes, 1.01–1.04 for sesquiterpene photooxidation SOA, and 1.06–1.10 for the monoterpene and oxygenated terpene SOA. The GF of pure SOA (GForg) in experiments in which inorganic seed aerosol is used is determined by assuming volume-weighted water uptake (Zdanovskii-Stokes-Robinson or "ZSR" approach) and using the size-resolved organic mass fraction measured by the Aerodyne Aerosol Mass Spectrometer. Knowing the water content associated with the inorganic fraction yields GForg values. However, for each precursor, the GForg values computed from different HTDMA-classified diameters agree with each other to varying degrees. Comparing growth factors from different precursors, we find that GForg is inversely proportional to the precursor molecular weight and SOA yield, which is likely a result of the fact that higher-molecular weight precursors tend to produce larger and less hygroscopic oxidation products.
Aerosol activation and cloud processing in the global aerosol-climate model ECHAM5-HAM

A parameterization for cloud processing is presented that calculates activation of aerosol particles to cloud drops, cloud drop size, and pH-dependent aqueous phase sulfur chemistry. The parameterization is implemented in the global aerosol-climate model ECHAM5-HAM. The cloud processing parameterization uses updraft speed, temperature, and aerosol size and chemical parameters simulated by ECHAM5-HAM to estimate the maximum supersaturation at the cloud base, and subsequently the cloud drop number concentration (CDNC) due to activation. In-cloud sulfate production occurs through oxidation of dissolved SO2 by ozone and hydrogen peroxide. The model simulates realistic distributions for annually averaged CDNC although it is underestimated especially in remote marine regions. On average, CDNC is dominated by cloud droplets growing on particles from the accumulation mode, with smaller contributions from the Aitken and coarse modes. The simulations indicate that in-cloud sulfate production is a potentially important source of accumulation mode sized cloud condensation nuclei, due to chemical growth of activated Aitken particles and to enhanced coalescence of processed particles. The strength of this source depends on the distribution of produced sulfate over the activated modes. This distribution is affected by uncertainties in many parameters that play a direct role in particle activation, such as the updraft velocity, the aerosol chemical composition and the organic solubility, and the simulated CDNC is found to be relatively sensitive to these uncertainties.
In-situ comparison of the NOy instruments flown in MOZAIC and SPURT

Two aircraft instruments for the measurement of total odd nitrogen (NOy) were compared side by side aboard a Learjet A35 in April 2003 during a campaign of the AFO2000 project SPURT (Spurengastransport in der Tropopausenregion). The instruments albeit employing the same measurement principle (gold converter and chemiluminescence) had different inlet configurations. The ECO-Physics instrument operated by ETH-Zürich in SPURT had the gold converter mounted outside the aircraft, whereas the instrument operated by FZ-Jülich in the European project MOZAIC III (Measurements of ozone, water vapour, carbon monoxide and nitrogen oxides aboard Airbus A340 in-service aircraft) employed a Rosemount probe with 80 cm of FEP-tubing connecting the inlet to the gold converter. The NOy concentrations during the flight ranged between 0.3 and 3 ppb. The two data sets were compared in a blind fashion and each team followed its normal operating procedures. On average, the measurements agreed within 7%, i.e. within the combined uncertainty of the two instruments. This puts an upper limit on potential losses of HNO3 in the Rosemount inlet of the MOZAIC instrument. Larger transient deviations were observed during periods after calibrations and when the aircraft entered the stratosphere. The time lag of the MOZAIC instrument observed in these instances is in accordance with the time constant of the MOZAIC inlet line determined in the laboratory for HNO3.