Trace gas measurements at the monitoring station cape point,South Africa,between 1978 and 1988

Since 1978, a measuring station has been operated at Cape Point (34°21 S, 18°29 E). In this article, results of measurements of CO, CFCl₃, CCl₄, O₃, N₂O and CH₄ are presented as monthly means and analyzed with respect to long-term trends and seasonal variations. For CO and CH₄, very similar seasonal variations have been observed, indicating strong interrelations between these two gases. For CO and O₃, no significant changes of the mean annual concentrations can be established for the observation periods of 10 and 5 years, respectively. The measurements yield a growth rate of 9.1 pptv yr^-1 for CFCl₃ (1980–1987) and 0.6 ppbv yr^-1 for N₂O (1983–1987). The concentration increases of CH₄ (10.3 ppbv yr^-1 for 1983–1987) and of CCl₄ (2.1 pptv yr^-1 for 1980–1988) are analyzed for temporal changes during the last years.Presented at the Second Conference on Baseline Observations in Atmospheric Chemistry (SABOAC II) in Melbourne, Australia, November 1988.     

European sources of halocarbons and nitrous oxide: Update 1986

Semi-continuous measurements of CFCl₃, CF₂Cl₂, CCl₄, CH₃CCl₃ and N₂O were made at Adrigole, Ireland as part of the Atmospheric Lifetime Experiment (ALE). Clean, baseline air from the Atlantic Ocean was measured approximately 70% of the time; pollution events from Europe, for the remainder. The two final years of ALE data from Adrogole give a five-year record from July 1978 to June 1983. This paper extends previous work on the relative enhancements of trace gases during pollution episodes and presents (1) unambiguous identification of elevated levels of N₂O concurrent with halocarbon pollution events, (2) detection of trends in emission of CH₃CCl₃, (3) discovery of seasonal variations in emission of CF₂Cl₂, CCl₄ and CH₃CCl₃, (4) characterization of typical summer and winter pollution episodes, and (5) identification of weather patterns over Europe that are associated with high concentrations of CFCs at Adrigole. Some of these results assume that CFCl₃ represents a uniform, well buffered source from the continent. The latter two results are particularly useful in the testing and calibration of three-dimensional chemical transport models. Observed enhancements are marginally consistent with estimates of halocarbon use by the chemical industry. The source of nitrous oxide correlated with halocarbons is 0.8 Tg(N)/yr from Europe alone and represents approximately 10% of the global stratospheric loss.     

FTIR studies of reactions between the nitrate radical and haloethenes

Products and mechanisms for the gas-phase reactions of NO₃ radicals with CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂,cis-CHCl=CHCl andtrans-CHCl=CHCl in air have been studied. The experiments were carried out at 295±2 K and 740±5 Torr in a 480-L Teflon-coated reaction chamber and at 295±2 K and 760±5 Torr in a 250-L stainless steel reactor. NO₃ was generated by the thermal dissociation of N₂O₅. Experiments with¹⁵NO₃ and CD₂CDCl have also been performed. The initially formed nitrate peroxynitrates decay into carbonyl compounds, nitrates, HCl and ClNO₂. In adidtion, there are indications of nitrooxy acid chlorides being produced. The reactions with CH₂=CCl₂ and CHCl=CCl₂ are more complex due to release of chlorine atoms which eventually lead to formation of chloroacid chlorides.A general reaction mechanism is proposed and the observed concentration-time profiles of reactants and products are simulated for each compound. The rate constants for the initial step of NO₃ addition to the chloroethenes are determined as: (2.6±0.5, 9.4±0.9, 2.0±0.4 and 1.4±0.4) × 10^–16 cm³ molecule^–1 s^–1 for CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂ andcis-CHCl=CHCl, respectively.     

The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30° north latitude

The set of high-resolution infrared solar observations made with the Atmospheric Trace Molecule Spectroscopy (ATMOS)-Fourier transform spectrometer from onboard Spacelab 3 (30 April-1 May 1985) has been used to evaluate the total budgets of the odd chlorine and fluorine chemical families in the stratosphere. These budgets are based on volume mixing ratio profiles measured for HCl, HF, CH₃Cl, ClONO₂, CCl₄, CCl₂F₂, CCl₃F, CHClF₂, CF₄, COF₂, and SF₆ near 30° north latitude. When including realistic concentrations for species not measured by ATMOS, i.e., the source gases CH₃CCl₃ and C₂F₃Cl₃ below 25 km, and the reservoirs ClO, HOCl and COFCl between 15 and 40 km (five gases actually measured by other techniques), the 30° N zonal 1985 mean total mixing ratio of chlorine, Cl, was found to be equal to (2.58±0.10) ppbv (parts per billion by volume) throughout the stratosphere, with no significant decrease near the stratopause. The results for total fluorine indicate a slight, but steady, decrease of its volume mixing ratio with increasing altitude, around a mean stratospheric value of (1.15±0.12) ppbv. Both uncertainties correspond to one standard deviation. These mean springtime 1985 stratospheric budgets are commensurate with values reported for the tropospheric Cl and F concentrations in the early 1980s, when allowance is made for the growth rates of their source gases at the ground and the time required for tropospheric air to be transported into the stratosphere. The results are discussed with emphasis on conservation of fluorine and chlorine and the partitioning among source, sink, and reservoir gases throughout the stratosphere.     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 2. Model Chemistry and Comparison of Modelled CH4, CO, and O3 with Surface Measurements

In part two of this series of papers on the IMS model, we present the chemistry reaction mechanism usedand compare modelled CH₄, CO, and O₃ witha dataset of annual surface measurements. The modelled monthly and 24-hour mean tropospheric OH concentrationsrange between 5–22 × 10⁵ moleculescm^–3, indicating an annualaveraged OH concentration of about 10 × 10⁵ moleculescm^–3. This valueis close to the estimated 9.7 ± 0.6 × 10⁵ moleculescm^–3 calculated fromthe reaction of CH₃CCl₃ with OH radicals.Comparison with CH₄ generally shows good agreementbetween model and measurements, except for the site at Barrow where modelledwetland emission in the summer could be a factor 3 too high.For CO, the pronounced seasonality shown in the measurements is generally reproduced by the model; however, the modelled concentrations are lower thanthe measurements. This discrepancy may due to lower the CO emission,especially from biomass burning,used in the model compared with other studies.For O₃, good agreement between the model and measurements is seenat locations which are away from industrial regions. The maximum discrepancies between modelled results and measurementsat tropical and remote marine sites is about 5–10 ppbv,while the discrepancies canexceed 30 ppbv in the industrial regions.Comparisons in rural areas at European and American continental sites arehighly influenced by the local photochemicalproduction, which is difficult to model with a coarse global CTM.The very large variations of O₃ at these locations vary from about15–25 ppbv in Januaryto 55–65 ppbv in July–August. The observed annual O₃amplitude isabout 40 ppbv compared with about 20 ppbv in the model. An overall comparison of modelled O₃ with measurements shows thatthe O₃seasonal surface cycle is generally governed bythe relative importance of two key mechanisms that drivea springtime ozone maximum and asummertime ozone maximum.     

Ground-Based Atmospheric CO2, CH4, and CO Column Measurements at Golmud in the Qinghai-Tibetan Plateau and Comparisons with TROPOMI/S5P Satellite Observations

Measurements of carbon dioxide(CO₂), methane(CH₄), and carbon monoxide(CO) are of great importance in the Qinghai-Tibetan region, as it is the highest and largest plateau in the world affecting global weather and climate systems. In this study, for the first time, we present CO₂, CH₄, and CO column measurements carried out by a Bruker EM27/SUN Fourier-transform infrared spectrometer(FTIR) at Golmud(36.42°E, 94.91°N, 2808 m) in August 2021. The mean and...     

Ultraviolet absorption cross-sections of chloro and chlorofluoro-methanes at stratospheric temperatures

Absorption cross-sections of nine halomethanes (CCl₄, CHCl₃, CH₂Cl₂, CH₃Cl, CFCl₃, CF₂Cl₂, CF₃Cl, CHFCl₂, and CHF₂Cl), measured between 174 and 250 nm for temperatures ranging from 225 to 295 K, are presented with uncertainties ranging from 2 to 4% and compared with previous determinations made for comparable temperature ranges.The largest temperature effect which takes place near the absorption threshold, decreases the absorption cross-section up to 50% for highly chlorinated methanes, but is negligible for molecules highly stabilized by hydrogen and/or fluorine. Extrapolated values for temperatures of aeronomical interest are presented, as well as parametrical formulas which give absorption cross-section values for given wavelength and temperature ranges.     

Multi-species chemical data assimilation with the Danish Eulerian hemispheric model: system description and verification

Satellite retrievals of atmospheric composition provide a wealth of data on a global scale. These complement results from atmospheric chemistry-transport models (CTMs), and can be combined using data assimilation. We present two assimilation schemes coupled to the Danish Eulerian Hemispheric Model (DEHM), a three-dimensional, off-line CTM with full photochemistry: a variant on the ensemble Kalman filter and the three-dimensional variational scheme. The aim of this paper is to describe the two schemes and present an initial assessment of their impacts on model skill. Retrievals of multiple atmospheric trace gases are assimilated, namely: NO₂ tropospheric column densities, CH₄ total column densities, and partial column concentrations of O₃, CO and CH₄; these data are retrieved from four satellite sensors. Data for each species are assimilated independently of one another, and other species are only adjusted indirectly via the model’s chemistry and dynamics. Assimilation results are compared with measurements from surface monitoring stations and other satellite retrievals, and preliminary validation results are presented.Reference simulations (without assimilation) grossly underestimate surface CO concentrations, and both assimilation schemes eliminate this large and systematic model bias. The assimilation improves the spatial correlation of modelled CO with surface observations, and improves the spatial correlation between forecasts and retrievals for CO, NO₂ and O₃. Results for CH₄ show a loss of skill due to a mismatch in model bias between two assimilated CH₄ data-sets. Finally, we discuss differences in methodology and results between this paper and a recent study on multi-species chemical data assimilation. Joint optimisation of initial conditions and emission rates offers a promising direction for improving modelled boundary-layer concentrations.     

Reactions of chlorine atoms and hydroxyl radicals with trichloroethanol: a mechanistic and kinetic study

The multi-channel reactions (1) CCl₃CH₂OH+Cl→ products and (2) CCl₃CH₂OH+OH→ products have been investigated by using the dual-level direct dynamics method. Two reaction channels, i.e., methylene- and hydroxyl-hydrogen abstraction, are identified for each reaction. The optimized geometries and frequencies of the stationary points are calculated at the B3LYP/6-311G(d,p) and MP2/6-311G(d,p) levels. Higher-level energies are obtained at the MC-QCISD and G3(MP2) levels based on the B3LYP and MP2 geometries, respectively, as well as by the CCSD(T)/6-31G(d)+CF method using the B3LYP geometries. Complexes with energies lower than those of the reactants are located at the entrance of each reaction channel. The rate constants for each reaction channel are evaluated by using the canonical variational transition state theory (CVT) incorporating the small-curvature tunneling (SCT) correction in a temperature range of 200–2000 K at the MC-QCISD//B3LYP/6-311G(d,p) level. The agreement of the calculated rate constants and experimental values for two reactions is seen to be remarkably good. Theoretical results indicate that in a low temperature range, the branching ratio to the hydroxyl-H-abstraction channel for both reactions is found negligible. The reactions proceed practically via methylene-H-abstraction yielding the products of CCl₃CHOH+HCl and CCl₃CHOH+H₂O, respectively; while for reaction of CCl₃CH₂OH+Cl, hydroxyl-H-abstraction channel appears to be probable with the increase of temperature. The enthalpies of formation for the CCl₃CH₂OH, CCl₃CHOH, and CCl₃CH₂O species are evaluated via isodesmic reactions at several levels.     

Field study of the emissions of methyl chloride and other halocarbons from biomass burning in Western Africa

A field study of trace gas emissions from biomass burning in Equatorial Africa gave methyl chloride emission ratios of 4.3×10^–5±0.8×10^–5 mol CH₃Cl/mol CO₂. Based on the global emission rates for CO₂ from biomass burning we estimate a range of 226–904×10⁹ g/y as global emission rate with a best estimate of 515×10⁹ g/y. This is somewhat lower than a previous estimate which has been based on laboratory studies. Nevertheless, our emission rate estimates correspond to 10–40% of the global turnover of methyl chloride and thus support the importance of biomass burning as methyl chloride source. The emission ratios for other halocarbons (CH₂Cl₂, CHCl₃, CCl₄, CH₃CCl₃, C₂HCl₃, C₂Cl₄, F-113) are lower. In general there seems to be a substantial decrease with increasing complexity of the compounds and number of halogen atoms. For dichloromethane biomass burning still contributes significantly to the total global budget and in the Southern Hemisphere biomass burning is probably the most important source for atmospheric dichloromethane. For the global budgets of other halocarbons biomass burning is of very limited relevance.     

NUMERICAL SIMULATION OF ATMOSPHERIC METHANE TRENDS OVER THE LAST 150 YEARS*

A global two-dimensional chemistry model is developed to study long-term trends of CH₄ since industrial revolution.The sources of CH₄,CO and NO_x are parameterized as functions of latitude and time.With two long-term emission scenarios,long-term trends of CH₄ are simulated.The results have a good agreement with observation from ice cores.The modeled CH₄ increased from 760 ppbv in 1840 to 1611.9 ppbv in 1991, while the modeled number concentration of tropospheric OH decreased from 7.17×10⁵ cm^-3 in 1840 to 5.79×10⁵ cm^-3 in 1991.The increase of atmospheric CH₄ can be explained by the increase of emission of CH₄ and build-up because of decrease of OH radicals that remove CH₄ from the atmosphere.The model is also used to simulate the distribution of CH₄.Comparisons between the model results and observations show that the model can simulate both latitudinal distribution and seasonal variation of CH₄ well.     

Estimates of indirect global warming potentials for CH4, CO and NOX

Emissions may affect climate indirectly through chemical interactions in the atmosphere, but quantifications of such effects are difficult and uncertain due to incomplete knowledge and inadequate methods. A preliminary assessment of the climatic impact of changes in tropospheric O₃ and CH₄ in response to various emissions is given. For a 10% increase in the CH₄ emissions the relative increase in concentration has been estimated to be 37% larger. The radiative forcing from enhanced levels of tropospheric O₃ is estimated to 37% of the forcing from changes in CH₄. Inclusion of indirect effects approximately doubles the climatic impact of CH₄ emissions. Emissions of NO_x increase tropospheric O₃, while the levels of CH₄ are reduced. For emissions of NO_x from aircraft, the positive effects via O₃ changes are significantly larger than the negative through changes in CH₄. For NO_x emitted from surface sources, the effects through changes in O₃ and CH₄ are estimated to be of similar magnitude and large uncertainty is connected to the sign of the net effect. Emissions of CO have positive indirect effects on climate through enhanced levels of tropospheric o₃ and increased lifetime of CH₄. These results form the basis for estimates of global warming potentials for sustained step increases in emissions.     

Chlorine initiated oxidation studies of hydrochlorofluorocarbons: Results for HCFC-123 (CF3CHCl2) and HCFC-141b (CFCl2CH3)

Oxidation reactions of the proposed CFC substitutes HCFC-123 (CF₃CHCl₂) and HCFC-141b (CFCl₂CH₃) have been studied in the laboratory using long-path Fourier transform infrared spectroscopy. The air oxidation of the HCFCs was initiated by the photolysis of Cl₂ forming Cl atoms that abstract H atoms from the HCFC. CF₃C(O)Cl was the only carbon containing compound observed in the infrared spectrum of the products of the HCFC-123/Cl₂ irradiations and its yield was approximately one. The product data are consistent with formation of CF₃C(O)Cl by Cl elimination of the intermediate halogenated alkoxy radical CF₃CCl₂O. The Cl-initiated oxidation of HCFC-141b led to the formation of CO and C(O)FCl. The product data are consistent with a 1 : 1 relationship between C(O)FCl formed and HCFC-141b reacted. Product data were compatible with both decomposition by cleavage of the C–C bond of the radical CFCl₂CH₂O leading to the prompt generation of C(O)FCl and reaction of the radical with O₂ forming the two carbon halogenated aldehyde CFCl₂CH(O), which in the presence of Cl was likely oxidized to C(O)FCl. An approximate method was developed in which the ratio was extracted from analysis of the time evolution of HCFC-141b, C(O)FCl, and CO. The data suggest that the contributions are comparable.     

Distributions of O3, CO and NMHCs over the rural sites in central India

The surface level measurements of O₃, CO, CH₄ and light NMHCs were made at eight different rural sites in the central part of India during February, 2004. The online analyzer was used for in-situ measurement of O₃ while air samples were collected for the analyses of CO, CH₄ and NMHCs using the gas chromatography techniques. The average mixing ratios of O₃, which were in the range of 60–90 ppbv, are significantly higher compared to the typical values reported for urban sites of India. The increase rates of O₃ in the forenoon hours were estimated to be in the range of about 8.8–10 ppbv h⁻¹. The slopes of ∆O₃/∆CO, which is an indicator of the efficiency of photochemical production, were in the range of 0.24–0.33 ppbv ppbv⁻¹. However, levels of primary pollutants e.g., NMHCs, CO, etc. at these sites were much lower than urban sites, but higher compared to previously observed values surrounding marine region of India. The estimated ratios of NMHCs and CO indicate fossil fuel combustion process as the dominant source of primary pollutants in this corridor.     

Trace Gas Measurements Between Moscow and Vladivostok Using the Trans-Siberian Railroad

Using a laboratory wagon traveling along the Trans-Siberian railroad, O₃, NO, NO₂, CO, CH₄, SF₆ and black carbon aerosol have been measured during the summer of 1996. The expedition from Niznij Novgorod (500 km east of Moscow) to Vladivostok (and back to Moscow) has shown the great potential of the train method; here the first results are presented and discussed. A wealth of boundary layer air data was obtained during the over 18000 km travel without serious contamination problems from the electric train itself. The diurnal O₃ cycle peaked generally below 50 nmole/mole, showed the effects of changes in J(NO₂), and often dropped to a few nmole/mole at night time during inversions. Over the vast Siberian lowlands situated between the Ural mountains and the river Yenisey, CH₄ levels were consistently elevated at around 1.95 µmole/mole, which we mainly attribute to wetland emissions. Over eastern Siberia, however, CH₄ levels were generally lower at 1.85 µmole/mole. In contrast, over the west Siberian lowlands, CO levels were relatively low, often reaching values of only 110 nmole/mole, whereas over eastern Siberia CO levels were higher. Very high CO levels were detected over a 2000 km section east of Chita, along the river Amur, which represented an enormous polluted air mass. ¹⁴C analysis performed on several CO samples confirms that the origin was biomass burning. SF₆, which was measured as a general conserved tracer, showed an eastward attenuation from 4.0 to 3.9 pmole/mole, with peaks in a number of places due to local Russian emissions.     

Modeling the sudden decrease in CH4 growth rate in 1992

A two-dimensional global chemistry model is developed to study the distribution and long-term trends of methane. The model contains 34 species and 104 chemical and photochemical reactions. Using the model, the long-term trends of CH₄, CO and OH in atmosphere are simulated, comparison between the model and observations shows that the simulation is successful. Experiments are done to investigate the causes of dramatic decrease in the growth rate of CH₄ in 1992 such as OH increase due to stratospheric ozone depletion, decrease of temperature in the troposphere due to Mount Pinatubo eruption and descendent of CH₄ sources fluxes. A new explanation is proposed and verified by this model that the decrease of CO emission plays an important role for the abnormal growth rate of CH₄ in 1992. We find that the decreases of CH₄ and CO emissions are the main reasons for the sudden decrease of growth rate of CH₄ in 1992, which account for 73% and 27% respectively.     

Impacts of Global Emissions of CO, NOx, and CH4 on China Tropospheric Hydroxyl Free Radicals

Using the global chemistry and transport model MOZART,the simulated distributions of tropospheric hydroxyl free radicals(OH) over China and its sensitivities to global emissions of carbon monoxide(CO),nitrogen oxide(NO x),and methane(CH 4) were investigated in this study.Due to various distributions of OH sources and sinks,the concentrations of tropospheric OH in east China are much greater than in west China.The contribution of NO + perhydroxyl radical(HO 2) reaction to OH production in east China is more pronounced than that in west China,and because of the higher reaction activity of non-methane volatile organic compounds(NMVOCs),the contributions to OH loss by NMVOCs exceed those of CO and take the dominant position in summer.The results of the sensitivity runs show a significant increase of tropospheric OH in east China from 1990 to 2000,and the trend continues.The positive effect of double emissions of NO x on OH is partly offset by the contrary effect of increased CO and CH 4 emissions:the double emissions of NO x will cause an increase of OH of 18.1%-30.1%,while the increases of CO and CH 4 will cause a decrease of OH of 12.2%-20.8% and 0.3%-3.0%,respectively.In turn,the lifetimes of CH 4,CO,and NO x will increase by 0.3%-3.1% with regard to double emissions of CH 4,13.9%-26.3% to double emissions of CO and decrease by 15.3%-23.2% to double emissions of NO x.     

Estimation of Nocturnal Area Fluxes of Carbon Cycle Gases in Saint Petersburg Suburbs

Carbon dioxide, methane, and carbon monoxide are the carbon cycle gases, the data on their emissions are needed when monitoring air pollution and developing methods for reducing anthropogenic emissions to the atmosphere and for climate forecasting. The estimates of nocturnal area fluxes for CO₂, CH₄, and CO presented for a suburb of Saint Petersburg (Peterhof) are obtained using the box model and continuous observations of concentration of these gases. The mean values of CH₄, CO₂, and CO fluxes estimated for Peterhof for 2014–2015 are 44 ± 27, 6100 ± 4000, and 90 ± 100 t/(km² year), respectively. The intensity of the CO area flux has pronounced seasonal variations characterized by the maximum of ~(160 ± 120) t/(km² year) in November—February and by the minimum of ~(30 ± 20) t/(km² year) in June-July. The analysis of the ratio of CO/CO₂ fluxes identified the main types of anthropogenic sources typical of Peterhof: motor transport, natural gas combustion, and the use of wood stoves for the heating of private low-rise buildings (in the cold season).     

World-wide increase in tropospheric methane, 1978–1983

Tropospheric concentrations of methane in remote locations have averaged a yearly world-wide increase of 0.018±0.002 parts per million by volume (ppmv) during the period from January 1978 to December 1983. The concentrations in the north temperate zone are always greater than those in the south temperate zone by 7±1% because the major methane sources are all predominantly located in the northern hemisphere. The average world-wide tropospheric concentration of methane in dry air was 1.625 ppmv at the end of 1983, measured against an NBS standard certified as 0.97 ppmv (but with an accuracy of only ±1%). The world-wide concentration increases are described by a linear equation with a standard deviation of 0.003 ppmv for ten different collection periods during 1978–1983. The precision of measurement of the methane concentration in the atmospheric samples and in the standard was measured to be ±0.4% for each. Repetitive measurements of an air sample collected in November 1977 have shown the same concentration for six years with a standard deviation for these data of ±0.003 ppmv.The causes for the steady increase in methane concentration in the troposphere cannot be fixed with certainty from present data. Contributing causes can include increases in the source strengths from cattle and rice fields. The atmospheric concentrations of CO, CH₄ and HO are all closely coupled with one another, and increased concentrations of CO and/or CH₄ should cause reduced concentrations of HO, which in turn should lengthen the atmospheric lifetimes of CO and CH₄.Among other physical and chemical effects, a increase of 0.18 ppmv per decade should contribute a greenhouse warming of about 0.04°C per decade. Other secondary contributions to the greenhouse effect from increases in CH₄ may arise from methane-induced increases in stratospheric H₂O, in tropospheric O₃, and in numerous other trace species whose concentration is controlled by reaction with HO radicals.An increased CH₄ source strength may result from the effect of increasing atmospheric temperatures on the known aqueous biological CH₄ sources, such as swamps, and may be an added consequence of the greenhouse effect.     

Influence of the surface microlayer on the flux of nonconservative trace gases (CO,H2, CH4, N2O) across the ocean-atmosphere interface

Gas exchange experiments were conducted in the tropical Atlantic Ocean during a ship expedition with FS Meteor using a small rubber raft. The temporal change of the mixing ratios of CO, H₂, CH₄ and N₂O in the headspace of a floating glass box and the concentrations of these gases in the water phase were measured to determine their transfer velocities across the ocean-atmosphere interface. The ocean acted as a sink for these gases when the water was undersaturated with respect to the mixing ratio in the headspace. The transfer velocities were different for the individual gases and showed still large differences even when normalized for diffusivity. Applying the laminar film model, film thicknesses of 20 to 70 m were calculated for the observed flux rates of the different gas species. When the water was supersaturated with respect to atmospheric CO, H₂, CH₄ and N₂O, the transfer velocities of the emission process were smaller than those determined for the deposition process. In case of H₂ and CH₄, emission was even not calculable although, based on the observed gradient, the laminar film model predicted significant fluxes at the air-sea interface. The results are interpreted by destruction processes active within the surface microlayer.