TROPOZ II: Global distributions and budgets of methane and light hydrocarbons

One hundred atmospheric samples were collected aboard the French Caravelle research aircraft, during the TROPOZ II experiment (January 1991). Tropospheric meridional distributions versus height were then derived from 70° N to 60° S and between 0.25 km and 11 km for methane, acetylene, ethane and propane. Areas of significant emissions were identified over northern latitudes with, for acetylene, maximum mixing ratios in the north (1.896 ppbv) more than 70 times higher than in background southern latitudes (0.025 ppbv). The influence of emissions from biomass burning was also obvious in the tropical boundary layer. Significant dynamic phenomena led to high mixing ratio zones above 8 or 10 km even for the most reactive hydrocarbons.For the first time, simultaneous assessment of global tropospheric contents of several light hydrocarbons was carried out. Using TROPOZ II data (January 1991) and STRATOZ III data (June 1984) collected by Rudolph (1988) during similar aircraft flights in 1988, the following tropospheric loads (in Tg-compound) were estimated, in January 1991 and June 1984, respectively: 1.1 and 0.4 for acetylene, 5.0 and 3.9 for ethane, 3.6 and 1.4 for propane and 3545 for methane in January only. According to our results, 40 to 65% of acetylene and alkanes are oxidized in the tropics. In addition, by computing the annual tropospheric sink of acetylene and alkanes, an evaluation of their annual global fluxes was performed. The figures are, in Tg-compound y^-1 with an uncertainty of 80% to an order of magnitude, based on January and June data, respectively: 10 and 6.6 for acetylene, 16.3 and 17.6 for ethane and 52.3 and 26.5 for propane.     

Measurement of gaseous HNO3 over the Atlantic Ocean

A latitudinal profile (30° W, from 30° N to 30° S) of mixing ratios of nitric acid and particulate nitrate was determined on the Atlantic Ocean during the Polarstern cruise ANT VII/1 from Bremerhaven, Germany, to Rio Grande, Brazil. The detection of HNO₃ was performed simultaneously by laser-photolysis fragment-fluorescence (LPFF) and by nylon filter packs. The detection limit was about 30 pptv for a signal accumulation time of 1 h for LPFF and about 5 pptv for the filters at a collection time of 4 h. In general, the mixing ratios of HNO₃ in the Northern Hemisphere were found to be significantly higher than those in the Southern Hemisphere. The Atlantic background concentrations frequently varied between 80 pptv and the detection limit. Larger deviations from this trend were found for the more northern latitudes and for episodes like crossings of exhaust plumes from ships or from continental pollutions sources.     

Determination of selected atmospheric aromatic hydrocarbons at remote continental and oceanic locations using photoionization/flame-ionization detection

A new gas chromatographic technique with a modified photoionization detector connected in series with a conventional flame ionization detector was used to determine low concentrations of atmospheric hydrocarbons in remote atmospheres. Average mixing ratios of five aromatic hydrocarbons measured between 42°N and 30°S latitude in the Pacific Ocean in October/November 1983 were highest in the Northern Hemisphere. The average mixing ratios in the northern and southern marine atmospheres were 49±25 ppt (n=35) and 10±2 ppt (n=21) for benzene, 20±12 ppt (n=32) and 5.6±1.6 ppt (n=12) for toluene, 7.6±3.7 ppt (n=35) and 3.7±1.6 ppt (n=21) for ethylbenzene, 25±12 ppt (n=35) and 13±5 ppt (n=20) for the sum of m- and p-xylenes, and 14±6 ppt (n=35) and 6.6±3.0 ppt (n=21) for o-xylene, respectively. The first latitudinal gradients for these five aromatic compounds are reported. Benzene and toluene mixing ratios measured between July 1982 and October 1983 at a rural, mid-latitude continental site in eastern Washington state gave average values of 226±108 ppt and 133±84 ppt, respectively, with higher wintertime than summertime benzene levels. These continental samples gave calculated air mass ages averaging six days based on benzene-to-toluene ratios.     

Measurements of Carbon Monoxide and Nonmethane Hydrocarbons During POPCORN

During the field campaign POPCORN (Photo oxidant formation by plant emitted compounds and OH radicals in North-eastern Germany) in Pennewitt (Mecklenburg-Vorpommern, Germany) in August 1994, carbon monoxide and nonmethane hydrocarbons were measured over a large maize field by in-situ gas chromatography. Throughout the campaign CO and NMHC showed, even for a remote rural area, unexpectedly low mixing ratios. Except a few episodes, CO mixing ratios were around 120 ppb. Ethane was the only hydrocarbon showing mixing ratios exceeding 1 ppb. The mixing ratios of all other NMHC ranged between several hundred ppt and the lower limit of detection which was between 20 and 5 ppt depending on the compound. During three frontal passages CO and NMHC mixing ratios increased significantly, while between August 13 and 16, 1994, polar air masses were encountered with CO and NMHC mixing ratios dropping to values which are typical for North Atlantic background air. During this period average CO mixing ratios were 85 ppb and ethane as the most abundant hydrocarbon decreased to 650 ppt. The large-scale meteorological situation is reflected in an unusual frequency distribution of CO. The distribution shows three maxima which can be assigned to the periods of the frontal passages, to the observation of polar air masses and the rest of the campaign. Two-day backward trajectories were calculated in order to obtain information about the origin of the air masses transported to the site. The observed NMHC and CO data can be attributed to the origin of the air masses and the air mass trajectories. NMHC and CO mixing ratios were well correlated indicating that these compounds originated from similar mostly anthropogenic sources. An exception was isoprene which showed no correlation with CO. With values below 100 ppt the mixing ratio of isoprene, which is emitted by terrestrial vegetation, was also unexpectedly low during the first half of the campaign although the maximum temperatures were around 35°C.     

Hydrogen peroxide measurements in the marine atmosphere

Hydrogen peroxide, one of the key compounds in multiphase atmospheric chemistry, was measured on an Atlantic cruise (ANT VII/1) of the German research vessel Polarstern from 15 September to 9 October 1988, in rain and ambient air by a chemiluminescence technique. For gas phase H₂O₂ cryogenic sampling was employed. The presented results show an increase of gas-phase mixing ratios of about 45 pptv per degree latitude between 50° N and 0°, and a maximum of 3.5 ppbv around the equator. Generally higher mixing ratios were observed in the Southern Hemisphere, with a clear diurnal variation. The H₂O₂ mixing ratio is correlated to the UV radiation intensity and to the temperature difference between air and ocean surface water.     

Surface NO and NO2 mixing ratios measured between 30° N and 30° S in the Atlantic region

Surface NO and NO₂ mixing ratios were measured aboard the research vessel Polarstern during the mission ANT VII/1 from 24 September to 5 October 1988. The measurements were taken along the meridian at 30° W in the Atlantic region covering latitudes between 30° N and 30° S. The average mixing ratios were about 12 pptv NO/30 pptv NO₂ in the Northern Hemisphere and about 7 pptv NO/22 pptv NO₂ in the Southern. Elevated mixing ratios of 20 pptv NO/70 pptv NO₂ were found at 12° N (probably due to air masses originating from the surface of West Africa) and in the region of the ITCZ between 8° N and 5° N. Because of probable contamination by the ship, the measured mixing ratios mostly represent upper limits.     

Measurements of peroxyacetylnitrate in the marine boundary layer over the Atlantic

The atmospheric concentration of peroxyacetylnitrate (PAN) was measured during a cruise of the R.S. Polarstern from Bremerhaven (Germany) to Rio Grande do Sul (Brazil) in September/ October 1988. The measurements were made in-situ by a combination of electron capture gaschromatography with a cryogenic preconcentration step. The theoretical lower limit of detection (3) was 0.4 ppt. The mixing ratios of PAN varied by more than three orders of magnitude from 2000 ppt in the English Channel to less than 0.4 ppt south of the Azores (38° N). South of 35° N, PAN levels were below the detection limit, except at 30–31° S off the eastern coast of South America. Here, PAN mixing ratios of 10 to 100 ppt were detected in continentally influenced air masses. Detectable levels of PAN were mostly observed in air masses of continental or high northern origin. Changes in the wind directions were usually associated with substantial changes in the PAN mixing ratios.     

Light hydrocarbons in the surface water of the mid-Atlantic

During a cruise of RV Polarstern over the Atlantic in September/October 1988, C₂–C₄ hydrocarbons were measured in surface sea water. The ship passed through three different ocean regions divided by divergences at 8° N and 3° S. Hydrocarbon concentrations differed considerably in these regions. The highest values were obtained for ethene with mean concentrations of 246 pMol/l between 35° N and 8° N, 165 pMol/l between 8° N and 3° S, and 63 pMol/l between 3° S and 30° S. Low values were found for i- and n-butane and acetylene between 32 pMol/l and 1 pMol/l. The alkene concentrations were in general higher than the concentrations of their saturated homologs. Concentrations decreased with increasing carbon numbers. The various alkenes were well correlated with one another as were the various alkanes. Oceanic emission rates of the light hydrocarbons were calculated from their sea water concentrations using an ocean atmosphere exchange model. The averaged fluxes ranged from about 10⁸ molec cm^-2 s^-1 for the alkenes and ethane to less than 10⁷ molec cm^-2 s^-1 for the C₄ alkanes. Acetylene emissions were below 3×10⁶ molec cm^-2 s^-1. Based upon these rates budget estimates of NMHC in the ocean surface layer were made with a simple model considering production and destruction processes in the water. The emissions to the atmosphere appear to be the dominant loss process between 35° N and 8° N, whereas destruction in the water seems to be dominant in the latitude ranges 8° N-3° S and 3° S-30° S.     

Measurements of selected C2-C5 hydrocarbons in the background troposphere: Vertical and latitudinal variations

Meridional cross sections of the concentration of light hydrocarbons are reported. They were obtained from 20. April to 10. May, 1980, during the French research flight STRATOZ II, and cover the latitudes between 60° N and 60° S and the altitudes between 800 mb and 200 mb. The mixing ratios of ethane, ethene, acetylene, propane, propene, n-butane, i-butane, n-pentane, and i-pentane range between 2.0 and 0.02 ppb. Globally, a decrease in concentration with increasing altitude and -in most cases-with decreasing latitude is observed. In addition the 2-dimensional concentration fields show structures of different scales. In particular, isolated maxima of high concentrations are found in the upper troposphere. They point to fast vertical transport between the boundary layer and the upper troposphere. In the present case these maxima seem to be correlated with large scale meteorological systems, such as low pressure regions or the Inter Tropical Convergence Zone. It is argued that the NMHC provide a set of tracers well suited to the detection of fast vertical transport.     

Measurements of trace gases emitted by Australian savanna fires during the 1990 dry season

During 18–23 July 1990, 31 smoke samples were collected from an aircraft flying at low altitudes through the plumes of tropical savanna fires in the Northern Territory, Australia. The excess (above background) mixing ratios of 17 different trace gases including CO₂, CO, CH₄, several non-methane hydrocarbons (NMHC), CH₃CHO, NO _x (– NO + NO₂), NH₃, N₂O, HCN and total unspeciated NMHC and sulphur were measured. Emissionratios relative to excess CO₂ and CO, and emissionfactors relative to the fuel carbon, nitrogen or sulphur content are determined for each measured species. The emission ratios and factors determined here for carbon-based gases, NO _x , and N₂O are in good agreement with those reported from other biomass burning studies. The ammonia data represent the first such measurements from savanna fires, and indicate that NH₃ emissions are more than half the strength of NO _x emissions. The emissions of NO _x , NH₃, N₂O and HCN together represent only 27% of the volatilised fuel N, and are primarily NO _x (16%) and NH₃ (9%). Similarly, only 56% of the volatilised fuel S is accounted for by our measurements of total unspeciated sulphur.     

Net total and UV-B radiation at the sea surface

A three-week continuous record from 21 September to 5 October 1988 of solar and terrestrial downward and upward radiation flux densities (1 data set per minute) obtained during the Atlantic Ocean cruise of the R/V Polarstern (ANT VII/1) along 30° W between 30° N and 30° S is evaluated. As the cruise crossed both subtropics and tropics of the Atlantic Ocean, characteristic daily cycles and meridional distributions of the radiation components and atmospheric turbidity were obtained. Special attention is given to the ultraviolet component of global radiation. The influence of cloudiness on the radiation quantities is discussed. As the knowledge of the spatial and temporal distribution of solar and longwave atmospheric radiation at the sea surface is important for numerous meteorological, oceanographic, and physico-chemical investigations, this data set is compared with other measurements of the cruise. This work is the continuation of the measurements made during the cruise ANT V/5 of R/V Polarstern along 30° W between 40° S and 40° N in March/April 1987.     

Origins of atmospheric particulate matter over the North Sea and the Atlantic Ocean

During the ANT VII/1 cruise of the RV Polarstern from Bremerhaven (Germany) to Rio Grande do Sul (Brazil), atmospheric particulate matter was collected by bulk filtration with a time step of 36 hours. Elemental analyses were performed in order to determine atmospheric aerosol concentrations of Al, Si, P, S, K, Ca, Ti, Mn, Fe, and Zn over the North Sea, the Channel, and the North and South Atlantic. The slight and continuous moving in latitude, associated with the large variability in concentration levels and chemical composition, allow us to point out the relative influence of the major sources of particulate matter: desert soil-dust in the tropical North Atlantic, anthropogenic emissions in the North Sea and the Channel, and biomass burning and continental biogenic activity in the tropical South Atlantic.     

Sulfur emissions to the atmosphere from natural sourees

Emissions of sulfur gases from both natural and anthropogenic sources strongly influence the chemistry of the atmosphere. To assess the relative importance of these sources we have combined the measurements of sulfur gases and fluxes during the past decade to create a global emission inventory. The inventory, which is divided into 12 latitude belts, takes into account the seasonal dependence of sulfur emissions from biogenic sources. The total emissions of sulfur gases from natural sources are approximately 0.79 Tmol S/a. These emissions are 16% of the total sulfur emissions in the Northern Hemisphere and 58% in the Southern Hemisphere. The inventory clearly shows the impact of anthropogenic sulfur emissions in the region between 35° and 50°N.     

Regional Sources of Methyl Chloride, Chloroform and Dichloromethane Identified from AGAGE Observations at Cape Grim, Tasmania, 1998–2000

There are large uncertainties in identifying and quantifying the natural and anthropogenic sources of chloromethanes – methyl chloride (CH₃Cl), chloroform (CHCl₃) and dichloromethane (CH₂Cl₂), which are responsible for about 15% of the total chlorine in the stratosphere. We report two years of in situ observations of these species from the AGAGE (Advanced Global Atmospheric Gas Experiment) program at Cape Grim, Tasmania (41° S, 145° E). The average background levels of CH₃Cl, CHCl₃ and CH₂Cl₂ during 1998–2000 were 551± 8, 6.3± 0.2 and 8.9± 0.2 ppt (dry air mole fractions expressed in parts per 10¹²) respectively, with a two-year average amplitude of the seasonal cycles in background air of 25, 1.1 and 1.5 ppt respectively. The CH₃Cl and CHCl₃ records at Cape Grim show clear episodes of elevated mixing ratios up to 1300 ppt and 55 ppt respectively, which are highly correlated, suggesting common source(s). Trajectory analyses show that the sources of CH₃Cl and CHCl₃ that are responsible for these elevated observations are located in coastal-terrestrial and/or coastal-seawater regions in Tasmania and the south-eastern Australian mainland. Elevated levels of CH₂Cl₂ (up to 70 ppt above background) are associated mainly with emissions from the Melbourne/Port Phillip region, a large urban/industrial complex (population 3.5 million) 300 km north of Cape Grim.Now at the Centre for Atmospheric ChemistryNow at School of Environmental Sciences     

Impact of Non-Methane Hydrocarbons on Tropospheric Chemistry and the Oxidizing Power of the Global Troposphere: 3-Dimensional Modelling Results

The impact of natural and anthropogenicnon-methane hydrocarbons (NMHC) on troposphericchemistry is investigated with the global,three-dimensional chemistry-transport model MOGUNTIA.This meteorologically simplified model allows theinclusion of a rather detailed scheme to describeNMHC oxidation chemistry. Comparing model resultscalculated with and without NMHC oxidation chemistryindicates that NMHC oxidation adds 40–60% to surfacecarbon monoxide (CO) levels over the continents andslightly less over the oceans. Free tropospheric COlevels increase by 30–60%. The overall yield of COfrom the NMHC mixture considered is calculated to beabout 0.4 CO per C atom. Organic nitrate formationduring NMHC oxidation, and their transport anddecomposition affect the global distribution of NO _x and thereby O₃ production. The impact of theshort-lived NMHC extends over the entire tropospheredue to the formation of longer-lived intermediateslike CO, and various carbonyl and carboxyl compounds.NMHC oxidation almost doubles the net photochemicalproduction of O₃ in the troposphere and leads to20–80% higher O₃ concentration inNO _x -rich boundarylayers, with highest increases over and downwind ofthe industrial and biomass burning regions. Anincrease by 20–30% is calculated for the remotemarine atmosphere. At higher altitudes, smaller, butstill significant increases, in O₃ concentrationsbetween 10 and 60% are calculated, maximizing in thetropics. NO from lightning also enhances the netchemical production of O₃ by about 30%, leading to asimilar increase in the global mean OH radicalconcentration. NMHC oxidation decreases the OH radicalconcentrations in the continental boundary layer withlarge NMHC emissions by up to 20–60%. In the marineboundary layer (MBL) OH levels can increase in someregions by 10–20% depending on season and NO _x levels.However, in most of the MBL OH will decrease by10–20% due to the increase in CO levels by NMHCoxidation chemistry. The large decreases especiallyover the continents strongly reduce the markedcontrasts in OHconcentrations between land and oceanwhich are calculated when only the backgroundchemistry is considered. In the middle troposphere, OHconcentrations are reduced by about 15%, although dueto the growth in CO. The overall effect of thesechanges on the tropospheric lifetime of CH₄ is a 15%increase from 6.5 to 7.4 years. Biogenic hydrocarbonsdominate the impact of NMHC on global troposphericchemistry. Convection of hydrocarbon oxidationproducts: hydrogen peroxides and carbonyl compounds,especially acetone, is the main source of HO _x in theupper troposphere. Convective transport and additionof NO from lightning are important for the O₃ budgetin the free troposphere.     

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.     

A one-dimensional photochemical model of the troposphere with planetary boundary-layer parameterization

The results from a one-dimensional photochemical model of the troposphere representative of summertime conditions at Northern Hemisphere mid-latitudes are presented. A parameterization of mixing processes within the planetary boundary layer (PBL) has been incorporated into the model for both the daytime convective PBL and the formation of the nocturnal PBL. One result of the parameterized PBL is that the concentrations of some trace species in the free troposphere are 20–30% higher than when mixing processes are described by a vertical eddy diffusion coefficient which is held constant with respect to height and time.The calculations indicate that the lifetime of the oxides of nitrogen (NO _x =NO+NO₂) against photochemical conversion to nitric acid (HNO₃) during summertime conditions is on the order of 6 h. This lifetime is short enough to deplete most of the NO _x in the PBL, resulting in the finding that other reactive nitrogen species (HNO₃ and peroxyacetyl nitrate) are more abundant than NO _x throughout the free troposphere, even though NO _x is the most abundant reactive nitrogen species at the surface. The effects of the inclusion of anthropogenic nonmethane hydrocarbon (NMHC) chemistry are also discussed. The inclusion of NMHC chemistry has a pronounced effect on the photochemistry of tropospheric oxone and increases thein situ column production by more than 30%.     

NMHC in the marine atmosphere: Preliminary results of monitoring at Amsterdam Island

Between January 1984 and May 1987, C₂ to C₅ NMHC concentrations, and Radon-222 activities were measured at Amsterdam Island in the Indian Ocean. A large variability of about one order of magnitude was observed in the NMHC concentrations. Most of the samples were collected under marine influence. Using ethene as a reference compound for marine emissions, it appears that the NMHC/ethene composition of the air and its variability directly reflect the composition of dissolved gases in surface seawater. Only the ethane/ethene ratio presents a significant deviation from this typical composition and this can be attributed to a continental component. At sea level, the reation frequency of OH radicals with the NMHC is similar to that of methane and carbon monoxide. Thus, the contribution of marine NMHC should be taken into account in the modelling of oxidants in remote atmospheres.     

Characterization of C2−C4 NMHCs distributions at a high altitude tropical site in India

Air samples were collected covering a full diurnal cycle during each month of the year 2002 at a mountaintop of Mt. Abu (24.6^∘ N, 72.7^∘ E, 1680 amsl). These samples were analyzed for C₂−C₄ NMHCs using a gas chromatograph (GC) equipped with flame ionization detector (FID). The seasonally averaged diurnal distributions of these NMHCs do not show significant variations in the summer season. While sharp peaks in the diurnal variation of some species during evening hours are additional features apart from higher levels in all NMHCs in the winter season. The seasonal variations in relatively long lived species (e.g. ethane, propane and acetylene) are observed to be more pronounced compared to those in reactive species (e.g. ethene, propene and butanes). The seasonal changes in transport patterns seem to be more dominant factor at this site for the observed variations in NMHCs than changes in OH radical concentration. The annual mean mixing ratios of ethane, ethene, propane, propene, i-butane, acetylene, and n-butane are 1.22 ± 0.58, 0.34 ± 0.24, 0.46 ± 0.20, 0.17 ± 0.14, 0.21 ± 0.18, 0.41 ± 0.43, and 0.31 ± 0.35 ppbv, respectively. Only few pairs of NMHCs are observed to show good correlations, mainly due to transport of air masses with different degree of photochemical processing. A comparison of this measurement with data reported for other remote sites of the globe indicates lower levels of light NMHCs in the tropical sites. The annual mean mixing ratios of various C₂−C₄ NMHCs at Mt. Abu are lower by factors ranging between 3 to 9 compared to a nearest urban site of Ahmedabad. The annual mean propylene (propene) equivalent concentrations of about 1.12 and 8.62 ppbC were calculated for Mt. Abu and Ahmedabad, respectively.     

Methane,carbon monoxide and light non-methane hydrocarbon emissions from African savanna burnings during the FOS/DECAFE experiment

Atmospheric samples from savanna burnings were collected in the Ivory Coast during two campaigns in January 1989 and January 1991. About 30 nonmethane hydrocarbons from C₂ to C₆, carbon monoxide, carbon dioxide and methane were measured from the background and also at various distances from the burning. Concentrations in the fire plume reached ppmv levels for C₂-C₄ hydrocarbons, and 5300, 500 and 93 ppmv for CO₂, CO and CH₄ respectively. The excess in the mixing ratios of these gases above their background level is used to derive emission factors relative to CO and CO₂. For the samples collected immediately in the fire plume, a differentiation between high and low combustion efficiency conditions is made by considering the CO/CO₂ ratio. Ethene (C₂H₄), acetylene (C₂H₂), ethane (C₂H₆) and propene (C₃H₆) are the major NMHC produced in the flaming stage, whereas a different pattern with an increasing contribution of alkanes is observed in samples typical of post flaming processes. A strong correlation between methane and carbon monoxide suggests that these compounds are produced during the same stage of the combustion. In samples collected at a distance from the fire and integrated over a period of 30 minutes, the composition is very similar to that of flaming. NMHC/CO₂ is of the order of 0.7%, CH₄/CO₂ of the order of 0.4% and CO/CO₂ of the order of 6.3%. From this study, a global production by African savanna fires is derived: 65 Tg of CO-C, 4.2 Tg of CH₄-C and 6.7 Tg of NMHC-C. Whereas acetylene can be used as a conservative tracer of the fire plumes, only ethene, propene and butenes can be considered in terms of their direct photochemical impact.