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.     

Tropospheric ozone and oxides of nitrogen over the north-western Pacific in summer

In summer, atmospheric ozone was measured from an aircraft platform simultaneously with nitric oxide (NO), oxides of nitrogen (NO _y ), and water vapor over the Pacific Ocean in east Asia from 34° N to 19° N along the longitude of 138±3°E. NO _y was measured with the aid of a ferrous sulfate converter. The altitude covered was from 0.5 to 5 km. A good correlation in the smoothed meridional distributions between ozone and NO _y was seen. In particular, north of 25° N, ozone and NO _y mixing ratios were considerably higher than those observed in tropical marine air south of 25° N. NO _y and O₃ reached a minimum of 50 pptv and 4 ppbv respectively in the boundary layer at a latitude of 20° N. The NO concentration between 2 and 5 km at the same latitude was 30 pptv. The profiles of ozone and water vapor mixing ratios were highly anti-correlated between 25° N and 20° N. In contrast, it was much poorer at the latitude of 33° N, suggesting a net photochemical production of ozone there.     

On the Spatial Distribution and Seasonal Variation of Lower-Troposphere Ozone over Europe

Surface ozone data from 25 Europeanlow-altitude sites and mountain sites located between79°N and 28°N were studied. The analysiscovered the time period March 1989–February 1993.Average summer and winter O₃ concentrations inthe boundary layer over the continent gave rise togradients that were strongest in the north-west tosouth-east direction and west-east direction, respectively. WintertimeO₃ ranged from 19 to 27 ppbover the continent, compared to about 32 ppb at thewestern border, while for summer the continentalO₃ values ranged between 39 and 56 ppb and theoceanic mixing ratios were around 37 ppb. In the lowerfree troposphere average wintertime O₃ mixingratios were around 38 ppb, with only an 8 ppbdifference between 28°N and 79°N. For summerthe average O₃ levels decreased from about 55 ppbover Central Europe to 32 ppb at 79°N. Inaddition, O₃ and O_x(= O₃ + NO₂)in polluted and clean air were compared. Theamplitudes of the seasonal ozone variations increasedin the north-west to south-east direction, while thetime of the annual maximum was shifted from spring (atthe northerly sites) to late summer (at sites inAustria and Hungary), which reflected the contributionof photochemical ozone production in the lower partsof the troposphere.     

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.     

Latitudinal variation of measured NO2 photolysis frequencies over the Atlantic Ocean between 50° N and 30° S

Using a filter radiometer, the meridional profile of the NO₂ photolysis frequency, J(NO₂), was measured between 50° N and 30° S during the cruise ANTVII/1 September/October 1988 of the research vessel Polarstern on the Atlantic Ocean. Simultaneously, global broadband irradiance and acrosol were monitored. Clean marine background air with low aerosol loads (b _sp=(1–2)×10^-5 m^-1) was encountered at the latitudes 25° N–30° N and 18° S–27° S, respectively. Under these conditions and an almost cloudless sky J(NO₂) reached 7.3×10^-3 s^-1 (2 sr) for a zenith angle of 30°. Between 30° N and 30° S, the latitudinal variation of the J(NO₂) noontime maxima was less than ± 10%, while the mean value at noon was 7.8×10^-3 s^-1. For the set of all data between 50° N and 30° S, a nearly linear correlation of J(NO₂) vs. global broadland irradiance was found. The slope of (8.24±0.03)×10^-5 s^-1/mW cm^-2 agrees within 10% with observations in Jülich (51° N, 6.2° E).     

Isoprene and Its Oxidation Products Methyl Vinyl Ketone, Methacrolein, and Isoprene Related Peroxides Measured Online over the Tropical Rain Forest of Surinam in March 1998

Airborne measurements of volatile organic compounds (VOC) were performed overthe tropical rainforest in Surinam (0–12 km altitude,2°–7° N, 54°–58° W) using the proton transferreaction mass spectrometry (PTR-MS) technique, which allows online monitoringof compounds like isoprene, its oxidation products methyl vinyl ketone,methacrolein, tentatively identified hydroxy-isoprene-hydroperoxides, andseveral other organic compounds. Isoprene volume mixing ratios (VMR) variedfrom below the detection limit at the highest altitudes to about 7 nmol/molin the planetary boundary layer shortly before sunset. Correlations betweenisoprene and its product compounds were made for different times of day andaltitudes, with the isoprene-hydroperoxides showing the highest correlation.Model calculated mixing ratios of the isoprene oxidation products using adetailed hydrocarbon oxidation mechanism, as well as the intercomparisonmeasurement with air samples collected during the flights in canisters andlater analysed with a GC-FID, showed good agreement with the PTR-MSmeasurements, in particular at the higher mixing ratios.Low OH concentrations in the range of 1–3 × 10⁵molecules cm^-3 averaged over 24 hours were calculated due to lossof OH and HO₂ in the isoprene oxidation chain, thereby stronglyenhancing the lifetime of gases in the forest boundary layer.     

Variations in atmospheric CO2 at the Meteorological Research Institute, Tsukuba, Japan

Since April 1986, measurements of the CO₂ concentration in the surface air have been conducted at the Meteorological Research Institure (MRI, 36°04 N, 140°07 E, 25 m above sea level) in Tsukuba, located 50 km northeast of Tokyo, Japan. The CO₂ data measured over times between 11:00 Japan Standard Time (JST) and 16:00 JST (C _N ) were considered to be representative of the air (within a few ppmv) in the planetary boundary layer. To evaluate the representative CO₂ level on a spatial scale larger than that of the C _N record, the CO₂ data with hour-to-hour variation less than 1 ppmv were selected (C _P ). Comparison of these data with those of Ryori (39°02 N, 141°50 E), a continental station operated by the Japan Meteorological Agency, indicates that the C _P record provides a representative CO₂ level in the air on spatial scales of at least a few hundred kilometers.The C _N record allows an investigation of the internanual changes in photosynthesis/respiration against changes in climatological parameters. Within a small temperature anomaly (ca.±1 °C) respiration is sensitive to the temperature change, while photosynthesis is less sensitive. When the temperature anomaly is large, however, photosynthesis and respiration tend to be competitive.     

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.     

Stratospheric and total NO2 column measurements with a modified Canterbury filter photometer

A programme of ground-based stratospheric and total NO₂ column measurements was instituted at the Laboratory of Atmospheric Physics (40.5° N, 22.9° E) in August 1985. We present here the results of the first two years of measurements with a modified Canterbury filter photometer, details of which are given in the text. The stratospheric NO₂ column, obtained at twilight during low local NO₂ levels, shows the seasonal variation with monthly mean values of about 6×10^-15 molec. cm^-2 in the summertime to about 2.2×10^-15 molec. cm^-2 in the wintertime. These measurements compare well with measurements obtained with different instruments by other groups at similar latitudes (about 40° N) but in different places. Also, the asymmetry of the evening-to-morning stratospheric NO₂ over Thessaloniki was found to be on the average equal to 1.58. Total NO₂ column over Thessaloniki has a pronounced seasonal variation with amplitude of 0.68 matm. cm which can be explained partly from measured local NO₂ sources which discharge in the mixing layer and partly from photolysis of the NO₂ reservoir species.     

Atmospheric Methyl Iodide at Cape Grim, Tasmania, from AGAGE Observations

Atmospheric mixing ratios of methyl iodide (CH₃I) and other methyl halides have been measured at Cape Grim, Tasmania (41°S, 145°E), since early 1998 as part of the Advanced Global Atmospheric Gases Experiment (AGAGE). This paper analyses about 1700 ambient air CH₃I measurements from the 14-month period (March 1998–April 1999). Mixing ratios peaked during the summer, despite faster photolytic loss, suggesting local oceanic emissions were about 2.2–3.6 times stronger in summer than in winter. Back trajectories show that CH₃I levels are strongly dependent on air mass origin, with highest mixing ratios in air from the Tasman Sea/Bass Strait region and lowest levels in air originating from the Southern Ocean at higher latitudes. CH₃I mixing ratios were not well correlated with other methyl halides in unpolluted marine air. The large variations with season and air mass origin suggest that high frequency, continuous data from key locations will make a significant contribution to the understanding of sources and sinks of this important short-lived atmospheric species.     

Vertical profiles of acetylene in the troposphere and stratosphere

Stratospheric measurements of acetylene up to altitudes of 30 km are presented. The air samples were collected during three different balloon flights, two of them at 44°N, one at 32°N using balloon borne, liquid neon-cooled, cryosamplers. Their acetylene concentration was measured in the laboratory by flame ionisation gaschromatography. The different profiles at 32°N and 44°N are discussed with respect to possible vertical exchange processes and compared with published model calculations.     

Tropospheric Ozone at High Latitudes in Clean and Polluted Air Masses, a Climatological Study

Several years of continuous measurements of surfaceozone at Norwegian monitoring sites are studied in aclimatological way. The monitoring sites are at rurallocations extending from 58°N, a few hundredkilometers from the European continent and into theArctic at 79°N. The ozone observations are sorted intoclasses of integrated NO_x emissions along 96 h backtrajectories. The average seasonal cycles of ozone areestimated for each class separately. The differencesindicate the change from the background air due toanthropogenic emissions. The average seasonal cycle ofozone in the cleanest air masses showed a maximum inspring and a minimum during summer and autumn at allsites, but the spring maximum was more pronounced atthe southernmost locations. Polluted air masses showedan ozone deficit during winter and a surplus duringsummer. The deviation from the background was clearlylinked to the integrated NO_x emission along thetrajectories. In summer the calculations indicate thatthe number of ozone molecules formed per NO_x moleculedrops with increasing emissions. The average seasonalcycle of ozone at Birkenes for different transportsectors indicate that the most pronounced ozoneformation takes place in air masses from E-Europe/Russia.     

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.     

Diurnal variation of atmospheric CO<Subscript>2</Subscript> concentration and δ<Superscript>13</Superscript>C in an urban atmosphere during winter—role of the Nocturnal Boundary Layer

The paper presents the importance of the Nocturnal Boundary Layer in driving the diurnal variability of the atmospheric CO₂ mixing ratio and the carbon isotope ratio at ground level from an urban station in India. Our observations are the first of their kind from this region. The atmospheric CO₂ mixing ratio and the carbon isotopic ratio were measured for both the morning (05:30–07:30 IST) and afternoon time (16:00–18:00 IST) air samples at 5 m above ground level in Bangalore city, Karnataka State (12° 58′ N, 77° 38′ E, masl = 920 m) for a 10 day period during the winter of 2008. We observed a change of ~7% the in CO₂ mixing ratio between the morning and afternoon time air samples. A stable isotope analysis of CO₂ from morning samples showed a depletion in the carbon isotope ratio by ~2‰ compared to the afternoon samples. Along with the ground-based measurement of air samples, data of radiosonde measurements were also obtained from the Indian Meteorological Department to identify the vertical atmospheric structure at different time in a day. We proposed the presence or absence of the NBL as a controlling factor for the observed variability in the mixing ratio as well as its isotopic composition. Here we used the Keeling model approach to find out the carbon isotope ratio for the local sources. The local sources have further been characterized as anthropogenic and biological respiration (in %) using a two-component mixing model. We also used a vertical mixing model based on the concept of the mixing of isotopically depleted (carbon isotope) “polluted air” (PA) with isotopically enriched “free atmospheric air” (FA) above. Using this modeling approach, the contribution of FA at ground level is being estimated for both the morning and afternoon time air samples.     

Local recent changes in extreme air temperature

Daily minimum and maximum air temperatures recorded in Naples (1872–1982) and in surrounding areas have been analysed in order to set up a statistical model for investigating climatic changes of extreme air temperature. We have analysed on various time-scales the mean values of minimum air temperature lower than the 10th percentile (Tmin₁₀) and the mean values of the maximum air temperature greater than the 90th percentile (Tmax₉₀). The results have shown for the city: (i) a significant secular trend both for yearly Tmin₁₀ and Tmax₉₀, mostly due to the process of urbanization, that is also responsible for (ii) the ascertained change in the character of the annual cycle, (iii) a reasonable ability to forecast winter Tmin₁₀ and summer Tmax₉₀ in statistical terms using a markovian model, and (iv) a significant 11-yr cycle with an amplitude of 0.5 °C directly related to solar activity which has never been succesfully determined before.     

Characteristics of turnover of carbonyl sulfide in four different soils

Release and uptake of carbonyl sulfide (OCS) were measured at 25°C in samples of three forest soils (BL, BW, PBE) and one soil from a rape field (RA). The soil samples were flushed with a constant flow of either air (oxic conditions) or nitrogen (anoxic conditions) containing defined concentrations of OCS. A cryogenic trapping technique with liquid argon (-186 °C) was used to collect gas samples for analysis in a gas chromatograph equipped with a flame-photometric detector. The dependence of net OCS fluxes between soil and atmosphere could be described by a simple model of simultaneous OCS production and OCS uptake. By using this model, production rates (P), uptake rate constants (k) and compensation concentrations (m _c ) of OCS could be determined as function of the soil type and the incubation conditions. Under oxic conditions, OCS production (P) and uptake were observed in all soils tested. However, the compensation concentrations (<166 ng l^-1; 1 ng OCS l^-1=0.41 ppbv) that were calculated from the model were high relative to the ambient OCS concentration (ca. 0.5 ppbv). The production rates (0.16–1.9 ng h^-1 g^-1 dw) that were actually measured when flushing the soil samples with air containing zero OCS were smaller than those (17–114 ng h^-1 g^-1 dw) calculated from the model. This observation was explained by two different concepts: one assuming the existence of a threshold concentration (m _t ) below which OCS was no longer consumed in the soil; the other assuming the existence of two different OCS consumption processes, of which only the process active at elevated OCS concentrations was covered by the experiments. The latter concept allowed the estimation of OCS compensation concentrations that were partially low enough to allow the uptake of atmospheric OCS by soil. Both OCS production and uptake in PBE soil were dependent on soil temperature (optimum 20 °C) indicating a microbial process. However, both production and consumption of OCS were not consistently inhibited by sterilization of the soil, suggesting that they were not exclusively due to microbiological processes. Under anoxic conditions, OCS was also produced, but was not consumed except in one soil (RA). Production of OCS in the soils was stimulated after addition of thiocyanate, but not thiourea, thiosulfate, thioglycolate, tetrathionate, sulfate, elemental sulfur, cysteine and methionine.     

The tropospheric distribution of formaldehyde during TROPOZ II

A series of 149 measurements of the HCHO mixing ratio were made between 0 and 10 km altitude and 70° N to 60° S latitude during TROPOZ II. The data show a vertical decrease of the HCHO mixing ratio with altitude at all latitudes and a broad latitudinal maximum in the HCHO mixing ratio between 30° N and 30° S at all altitudes. The measured mixing ratios of HCHO are considerably higher than those expected from CH₄ oxidation alone, but agree broadly with the average latitude by altitude distribution of HCHO derived by a 2D model including emissions of C₁–C₇ hydrocarbons. A number of the regional scale deviations of the measured HCHO distribution from the average modelled one can be explained in terms of the local wind field.     

An Assessment of HOx Chemistry in the Tropical Pacific Boundary Layer: Comparison of Model Simulations with Observations Recorded during PEM Tropics A

Reported are the results from a comparison of OH,H₂O₂CH₃OOH, and O₃ observationswithmodel predictions based on current HO_x–CH₄reaction mechanisms. The field observations are thoserecorded during the NASA GTE field program, PEM-Tropics A. The major focus ofthis paper is on thosedata generated on the NASA P-3B aircraft during a mission flown in the marineboundary layer (MBL) nearChristmas Island, a site located in the central equatorial Pacific (i.e.,2° N, 157° W). Taking advantage of thestability of the southeastern trade-winds, an air parcel was sampled in aLagrangian mode over a significantfraction of a solar day. Analyses of these data revealed excellent agreementbetween model simulated andobserved OH. In addition, the model simulations reproduced the major featuresin the observed diurnalprofiles of H₂O₂ and CH₃OOH. In the case ofO₃, the model captured the key observational feature whichinvolved an early morning maximum. An examination of the MBL HO_xbudget indicated that the O(¹D) + H₂Oreaction is the major source of HO_x while the major sinks involveboth physical and chemical processes involving the peroxide species,H₂O₂ and CH₃OOH. Overall, the generally goodagreement between modeland observations suggests that our current understanding ofHO_x–CH₄ chemistry in the tropical MBL isquite good; however, there remains a need to critically examine this chemistrywhen both CH₂O and HO₂are added to the species measured.     

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.     

CO2 climate sensitivity and snow-sea-ice albedo parameterization in an atmospheric GCM coupled to a mixed-layer ocean model

The snow-sea-ice albedo parameterization in an atmospheric general circulation model (GCM), coupled to a simple mixed-layer ocean and run with an annual cycle of solar forcing, is altered from a version of the same model described by Washington and Meehl (1984). The model with the revised formulation is run to equilibrium for 1 × CO₂ and 2 × CO₂ experiments. The 1 ×CO₂ (control) simulation produces a global mean climate about 1° warmer than the original version, and sea-ice extent is reduced. The model with the altered parameterization displays heightened sensitivity in the global means, but the geographical patterns of climate change due to increased carbon dioxide (CO₂) are qualitatively similar. The magnitude of the climate change is affected, not only in areas directly influenced by snow and ice changes but also in other regions of the globe, including the tropics where sea-surface temperature, evaporation, and precipitation over the oceans are greater. With the less-sensitive formulation, the global mean surface air temperature increase is 3.5 °C, and the increase of global mean precipitation is 7.12%. The revised formulation produces a globally averaged surface air temperature increase of 4.04 °C and a precipitation increase of 7.25%, as well as greater warming of the upper tropical troposphere. Sensitivity of surface hydrology is qualitatively similar between the two cases with the larger-magnitude changes in the revised snow and ice-albedo scheme experiment. Variability of surface air temperature in the model is comparable to observations in most areas except at high latitudes during winter. In those regions, temporal variation of the sea-ice margin and fluctuations of snow cover dependent on the snow-ice-albedo formulation contribute to larger-than-observed temperature variability. This study highlights an uncertainty associated with results from current climate GCMs that use highly parameterized snow-sea-ice albedo schemes with simple mixed-layer ocean models.The National Center for Atmospheric Research is sponsored by the National Science Foundation.