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.     

Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

Field measurements of NO and NO₂ emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO _x detector allowing the determination of minimum flux rates of 2 g N m^-2 h^-1 for NO and 3 g m^-2 h^-1 for NO₂.The NO and NO₂ flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO₂, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO₂. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO₂ emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO₂ equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO₂. The soil acted as a net sink for ambient air NO and NO₂ mixing ratios higher than the equilibrium values and a net source for NO and NO₂ mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO₂ are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m^-2 h^-1 for NO₂ and 8 g N m^-2 h^-1 for NO. The NO and NO₂ flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO₂.Application of mineral fertilizers increased the NO and NO₂ emission rates. Highest emission rates were observed for urea followed by NH₄Cl, NH₄NO₃ and NaNO₃. The fertilizer loss rates ranged from 0.1% for NaNO₃ to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO _x emission from soil is estimated to be 11 Tg N yr^-1. This figure is an upper limit and includes the emission of 7 Tg N yr^-1 from natural unfertilized soils, 2 Tg N yr^-1 from fertilized soils as well as 2 Tg N yr^-1 from animal excreta. Despite its speculative character, this estimation indicates that NO _x emission by soil is important for tropospheric chemistry especially in remote areas where the NO _x production by other sources is comparatively small.     

The latitudinal distribution of carbon monoxide across the pacific from California to Antarctica

The results of a research study of the carbon monoxide concentration from California to 90° S, Antarctica are presented. The data both extend and support other research studies of the latitudinal distribution of carbon monoxide in that higher concentrations are evident over the Northern Hemisphere than over the Southern Hemisphere. Carbon monoxide concentrations range between 50 to 60 ppb with a few peaks into the 60s in the latitudinal area south of the ITCZ and values of 80 ppb or higher at latitudes north of Hawaii. A comparison is also made of carbon monoxide and ozone concentrations along the flight tract between California and Antarctica, over the Ellsworth Mountains of Antarctica, and between 78° S and the South Pole. These ozone-carbon monoxide data show statistically significant negative correlations in the upper troposphere and lower stratosphere over Antarctica. It is believed that this is a good indication of mixing across the tropopause.     

Global distribution of gaseous mercury in the troposphere

Atmospheric mercury concentrations were measured during a nautical expedition on the Atlantic Ocean between Hamburg (54°N, 10°E) and Santo Domingo (20°N, 67°W). In addition, samples were taken during flights on a commerical aircraft in the upper and middle troposphere between 60°N and 55°S, mostly over the Pacific Ocean. The data obtained in the lower troposphere over the Northern Atlantic show considerable variation in the Hg concentrations, with values ranging between 1 and 11 ng/m³; the average concentration was found to be 2.8 ng/m³. The upper tropospheric data show an interhemispheric difference with average values of 1.45 ng/m³ and 1.08 ng/m³ in the Northern and Southern Hemisphere, respectively. This suggests that mercury production occurs predominantly over the continents both by natural and anthropogenic processes. The mercury content in aerosols was found to be 0.3 ng/m³, or one-tenth of the atmospheric concentration. The data indicate a mean residence time of mercury in the atmosphere of a few months to one year.     

Estimates of gross and net fluxes of carbon between the biosphere and the atmosphere from biomass burning

In order to estimate the production of charcoal and the atmospheric emissions of trace gases volatilized by burning we have estimated the global amounts of biomass which are affected by fires. We have roughly calculated annual gross burning rates ranging between about 5 Pg and 9 Pg (1 Pg = 10¹⁵ g) of dry matter (2–4 Pg C). In comparison, about 9–17 Pg of above-ground dry matter (4–8 Pg C) is exposed to fires, indicating a worldwide average burning efficiency of about 50%. The production of dead below-ground dry matter varies between 6–9 Pg per year. We have tentatively indicated the possibility of a large production of elemental carbon (0.5–1.7 Pg C/yr) due to the incomplete combustion of biomass to charcoal. This provides a sink for atmospheric CO₂, which would have been particularly important during the past centuries. From meager statistical information and often ill-documented statements in the literature, it is extremely difficult to calculate the net carbon release rates to the atmosphere from the biomass changes which take place, especially in the tropics. All together, we calculate an overall effect lof the biosphere on the atmospheric carbon dioxide budget which may range between the possibilities of a net uptake or a net release of about 2 Pg C/yr. The release of CO₂ to the atmosphere by deforestation projects may well be balanced by reforestation and by the production of charcoal. Better information is needed, however, to make these estimates more reliable.Now at the Max-Planck-Institute for Chemistry, Mainz, FRG.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

Vertical distribution of chlorofluoromethanes in the upper troposphere and lower stratosphere

Vertical profiles of CCl₄, CFCl₃, and CF₂Cl₂ mixing ratios in the upper troposphere and lower stratosphere have been measured on four flights with chartered aircraft, type HS 125. The flights were carried out in November and December 1976 over Europe at latitudes between 50 and 60°N. At least eight air samples were taken during each ascent and descent of the aircraft at altitudes between 7 and 12.5 km. The samples were analysed in the laboratory using gaschromatographic procedures. The results indicate a decrease of the CCl₄, CFCl₃, and CF₂Cl₂ mixing ratios above the tropopause. The observed average gradients in the stratosphere are 14 pptv/km for CCl₄, 12 pptv/km for CFCl₃ and 27.8 pptv/km for CF₂Cl₂. With exception of CFCl₃ these gradients are higher than those predicted by model calculations. Apparently, further sink mechanisms for CCl₄ and CF₂Cl₂ exist in the lower stratosphere not yet included in the models.     

Emission of nitrous oxide from temperate forest soils into the atmosphere

N₂O emission rates were measured during a 13-month period from July 1981 till August 1982 with a frequency of once every two weeks at six different forest sites in the vicinity of Mainz, Germany. The sites were selected on the basis of soil types typical for many of the Central European forest ecosystems. The individual N₂O emission rates showed a high degree of temporal and spatial variabilities which, however, were not significantly correlated to variabilities in soil moisture content or soil temperatures. However, the N₂O emission rates followed a general seasonal trend with relatively high values during spring and fall. These maxima coincided with relatively high soil moisture contents, but may also have been influenced by the leaf fall in autumn. In addition, there was a brief episode of relatively high N₂O emission rates immediately after thawing of the winter snow. The individual N₂O emission rates measured during the whole season ranged between 1 and 92 g N₂O-N m^–2 h^–1. The average values were in the range of 3–11 g N₂O-N m^–2 h^–1 and those with a 50% probability were in the range of 2–8 g N₂O-N m^–2 h^–1. The total source strength of temperate forest soils for atmospheric N₂O may be in the range of 0.7–1.5 Tg N yr^–1.