Characterization of carbon monoxide,methane and nonmethane hydrocarbons in emerging cities of Saudi Arabia and Pakistan and in Singapore

We investigate the composition of 63 C₂-C₁₀ nonmethane hydrocarbons (NMHCs), methane (CH₄) and carbon monoxide (CO), in Jeddah, Mecca, and Madina (Saudi Arabia), in Lahore, (Pakistan), and in Singapore. We established a database with which to compare and contrast NMHCs in regions where ambient levels and emissions are poorly characterized, but where conditions are favorable to the formation of tropospheric ozone, and where measurements are essential for improving emission inventories and modeling. This dataset will also serve as a base for further analysis of air pollution in Western Saudi Arabia including, but not limited to, the estimation of urban emissions and long range pollution transport from these regions. The measured species showed enhanced levels in all Saudi Arabian cities compared to the local background but were generally much lower than in Lahore. In Madina, vehicle exhaust was the dominant NMHC source, as indicated by enhanced levels of combustion products and by the good correlation between NMHCs and CO, while in Jeddah and Mecca a combination of sources needs to be considered. Very high NMHC levels were measured in Lahore, and elevated levels of CH₄ in Lahore were attributed to natural gas. When we compared our results with 2010 emissions from the MACCity global inventory, we found discrepancies in the relative contribution of NMHCs between the measurements and the inventory. In all cities, alkenes (especially ethene and propene) dominated the hydroxyl radical (OH) reactivity (k _OH) because of their great abundance and their relatively fast reaction rates with OH.     

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.     

Ozone and PAN Formation Inside and Outside of the Berlin Plume – Process Analysis and Numerical Process Simulation

During the BERLIOZ field phase on 20 July 1998 a 40 km wide ozone-plume 30 to 70 km north of Berlin in the lee of the city was detected. The ozone mixing ratio inside the plume was app. 15 ppb higher than outside, mainly caused by high ozone precursor emissions in Berlin, resulting in a net chemical ozone production of 6.5 ppb h^–1, which overcompensates ozone advection of –3.6 ppb h^–1 andturbulent diffusion of –1.1 ppb h^–1. That means, although moreozone leaves the control volume far in the lee of Berlin than enters it at the leeside cityborder and although turbulent diffusion causes a loss of ozone in the leeside control volume the chemical production inside the volume leads to a net ozone increase. Using a semi-Lagrangian mass budget method to estimate the net ozone production, 5.0 ppb h^–1 are calculated for theplume. This means a fraction of about 20% of ozone in the plume is producedby local emissions, therefore called `home made' by the Berlin emissions. For the same area KAMM/DRAIS simulations using an observation based initialisation, results in a net production rate between 4.0 and 6.5 ppbh^–1, while the threefold nested EURAD model gives 6.0 ppbh^–1. The process analysis indicates in many cases goodagreement (10% or better) between measurements and simulations not only in the ozone concentrations but also with respect to the physical and chemical processes governing the total change. Remaining differences are caused by different resolution in time and space of the models and measurements as well as by errors in the emission calculation.The upwind-downwind differences in PAN concentrations are partly similar to those of ozone, because in the BERLIOZ case they are governed mainly by photochemical production. While in the stable boundary layer at night and windward of Berlin 0.1 to 0.3 ppb are detected, in the centre of the plume at noon concentrations between 0.75 ppb and 1.0 ppb are measured. The O₃/PAN ratio is about 80 to 120 and thus due to the relatively lowPAN concentrations significantly higher than found in previous studies. The low PAN formation on 20 July, was mainly restricted by the moderate nonmethane hydrocarbon levels, whereas high PAN concentrations of 3.0 ppb on 21 July, are caused by local production in the boundary layer and by large scale advection aloft.     

Evaluation of Modeled Spatially and Temporarily Highly Resolved Emission Inventories of Photosmog Precursors for the City of Augsburg: The Experiment EVA and Its Major Results

Emission inventories of NO_x, CO, and individual volatile organic compounds (VOC), highly resolved in space and time, belong to the most important input parameters for chemistry and transport models (CTM) used for ozone prediction. Because of the decisive influence of the input quality on the outcome of CTM simulations, the quality of emission inventories has to be assessed. This paper presents an experimental evaluation of the highly resolved emission inventories for the city of Augsburg. The emissions of the city, determined in March and October 1998 using mass balance and tracer techniques, and derived from the measured receptor concentration ratios, were compared with emissions modeled from an emission inventory. The modeled CO emissions were in agreement with the measured ones within the combined experimental and model uncertainties. More detailed CO emission model simulations suggest that the tendency of calculated CO emissions being smaller than the measured ones may be due to higher traffic activity in Augsburg. Modeled NO_x emissions were in agreement with the measured ones within the combined experimental and model uncertainties. Large deviations between modeled and measured values have been found for some individual NMHC compounds. The measured NMHC emission fingerprints were dominated by mobile sources. Substantial model predicted NMHC emissions from the solvent use could not be detected by measurements suggesting that they may not be correctly represented by the emission model.     

Emission characteristic of ozone related trace gases at a semi-urban site in the Indo-Gangetic plain using inter-correlations

Measurements of surface O₃, CO, NO_x and light NMHCs were made during December 2004 at Hissar, a semi-urban site in the state of Haryana in north-west region of the Indo-Gangetic Plain (IGP). The night-time O₃ values were higher when levels of CO, NO and NO₂ were lower but almost zero values were observed during the episodes of elevated mixing ratios of CO (above 2000 ppbv) and NO_x (above 50 ppbv). Slopes derived from linear fits of O₃ versus CO and O₃ versus NO_x scatter plots were also negative. However, elevated levels of O₃ were observed when CO and NO_x were in the range of 200–300 ppbv and 20–30 ppbv, respectively. Slope of CO-NO_x of about 33 ppbv/ppbv is much larger than that observed in the US and Europe indicating significant impact of incomplete combustion processes emitting higher CO and lesser NO_x. Correlations and ratios of these trace gases including NMHCs show dominance of recently emitted pollutants mostly from biomass burning at this site.     

Verification of the Contribution of Vehicular Traffic to the Total NMVOC Emissions in Germany and the Importance of the NO3 Chemistry in the City Air

In 1997 and 1998 several field campaigns for monitoring non-methane volatile organic compounds (NMVOCs) and nitrogen oxides (NO_x) were carried out in a road traffic tunnel and in the city center of Wuppertal, Germany. C₂–C₁₀ aliphatic and aromatic hydrocarbons were monitored using a compact GC instrument. DOAS White and long path systems were used to measure aromatic hydrocarbons and oxygenated aromatic compounds. A formaldehyde monitor was used to measure formaldehyde. Chemiluminescence NO analysers with NO₂ converter were used for measuring NO and NO₂. The high mixing ratios of the NMVOCs observed in the road traffic tunnel, especially 2.9 ppbv phenol, 1.5ppbv para-cresol and 4.4 ppbv benzaldehyde, in comparison with themeasured background concentration clearly indicate that these compounds were directly emitted from road traffic. Para-Cresol was for the first timeselectively detected as primary pollutant from traffic. From the measured data a NMVOC profile of the tunnel air and the city air, normalised to benzene (ppbC/ppbC), was derived. For most compounds the observed city air NMVOC profile is almost identical with that obtained in the traffic tunnel. Since benzene originates mainly from road traffic emission, the comparison of the normalised emission ratios indicate that the road traffic emissions in Wuppertal have still the largest impact on the city air composition, which is in contrast to the German emission inventory. In both NMVOC profiles, aromatic compounds have remarkably large contributions of more than 40 ppbC%. In addtion, total NMVOC/NO_x ratios from 0.6 up to 3.0ppbC/ppb in the traffic tunnel air and 3.4± 0.5 in the city air of Wuppertal were obtained. From the observed para-cresol/toluene and ortho-cresol/toluene ratios in the city air, evidence was found thatalso during daytime NO₃ radical reactions play an important role in urban air.     

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.     

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.     

Enhancements of CO and O3 from burnings in sugar cane fields

The manual harvest of sugar cane requires the burning of its foliage. This burning has strongly increased in Brazil after the National Alcohol Program was started which substituted automobile gasoline engines for alcohol engines. Presently, the source strength per unit area of this rural pollution is comparable to the well-known biomass burning source in Amazonia. The observed concentrations of CO and O₃ in the rural area of the state of São Paulo during the 1988 burning season were twice as large as those reported from an aircraft experiment of 1985 for biomass burnings of the tropical rain forest. Results are reported from airplane measurements and from three fixed ground stations. Mixing ratios of ozone and carbon monoxide in the height range below 6 km are normally less than 40 and 100 ppbv, (parts per billion by volume), respectively, in the absence of burnings. A strong O₃ and CO layer was observed during the burning period with peak concentrations of 80 ppbv of ozone and 580 ppbv of CO at about 2 km. The concentrations of CH₄ and CO₂ were also large, 1756 ppbv and 409 ppmv, respectively, at 1500 m. During the dry season period of the experiment, the ground based O₃ average diurnal variations obtained at the rural sites were practically identical to the typical urban variation observed at São José dos Campos, with daytime ozone values between 45 and 60 ppbv. A second three-day airplane excursion to the surgar cane fields in the wet season of 1989 has produces results to be contrasted with the dry (burning) season of 1988 and 1989. Carbon monoxide concentrations were below 100 ppbv at all heights and ozone concentrations were around 30–40 ppbv. The maximum daytime concentrations at the ground station Bauru was 25 ppbv of O₃, and at Jaboticabal it was 35 ppbv of O₃, only one half of what was observed in the dry season.Universidade Estadual de São Paulo.     

Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign

Gas-phase H₂O₂, organic peroxides and carbonyl compoundswere determined at various sites from Mid-July to early August 1998 during the BERLIOZ campaign in Germany. The sites were located northwest of Berlin and were chosen to determine pollutants downwind of the city emissions during a summer smog episode. Hydrogen peroxide (H₂O₂),methyl hydroperoxide (MHP, CH₃OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH₂OOH) were quantified in air samples by commercial fluorimetric methods and classical HPLC with post-column derivatisation by horseradish peroxidase/p-hydroxyphenyl acetic acid and fluorimetric detection. Carbonyl compounds were determined in ambient air by a novel method based onO-pentafluorobenzyl hydroxylamine as derivatisation agent.Mixing ratio profiles of the hydroperoxides and the carbonyl compounds are reported for the intensive phase of the campaign, 20–21 July, 1998. Peroxides showed pronounced diurnal variations with peak mixing ratios in the early afternoon. At times, a second maximum was observed in the late afternoon. The major part of the H₂O₂ was formed throughrecombination reactions of HO₂ radicals, but there is some evidencethat H₂O₂ is also formed from ozonolysis ofanthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C₂ to C₁₀,isobutanal), unsaturated carbonyl compounds (methacrolein, methylvinylketone, acrolein), hydroxycarbonyl (glycolaldehyde, hydroxyacetone) and dicarbonyl compounds (glyoxal, methylglyoxal, biacetyl), aromatic compounds (benzaldehyde, o- and m-tolylaldehyde) and pinonaldehyde.     

Atmospheric concentrations of nonmethane hydrocarbons at a North European coastal site

Two years of individual nonmethane hydrocarbon (NMHC) measurements at a rural site close to the south coast of Norway show that there was a distinct annual cycle with a late winter maximum and late summer minimum in the slowly reacting NMHCs acetylene, ethane, propane and i- and n-butane. The average January—March concentrations were a factor 2–4 higher than the July-September concentrations. Also ethene, propene and the pentanes show a similar annual cycle, but the individual scatter in the measurements in particular of propene, is large. The highest concentrations of NMHC were found in winter for easterly transport on a regional scale (out to 1500 km from the site), and for southeasterly transport in the summer.     

Variation Characteristics of Ambient NMHCs at Shangdianzi and Lin''an Regional GAW Sites

In order to study the variation characteristics of concentration of the atmospheric non-methane hydrocarbons (NMHCs) in background area of China, the atmospheric concentrations of NMHCs were measured at Lin'an (LA) regional GAW (Global Atmosphere Watch) Station (30°250'N , 119° 440'E; 132.0 m ASL)and Shangdianzi (SDZ) regional GAW Station (40°190'N , 117°07'E; 286.5 m ASL) with the sorbent sorption/thermal desorption/gas chromatographic method. Totally 145 samples were collected during the period of October 2003 and July 2004. Among the 52 NMHC species of C2-C10 detected there were 26 alkanes,17 alkenes, and 9 aromatics. The average concentrations of total NMHCs (TNMHCs) at LA and SDZ were(238.5±126.0) 10-9C and (278.7±185.5) 10-9C, respectively. The results showed the ambient concentrations of TNMHCs at LA regional GAW Station increased notably over the last decade. The compositions of NMHCs at SDZ and LA were relatively similar. The proportions of alkanes, alkenes, and aromatics for SDZ and LA were in ranges of (27.3±4.0)%, (10.3±3.5)%, and (62.5±4.8)%,respectively, with features of vehicle exhaust emissions. The concentrations of NMHCs at the two sites showed obvious diurnal and seasonal variations. The TNMHC concentrations in October-November were high at the two sites, and relatively low in April and July. The diurnal variation patterns at the sites were different. The high TNMHC concentrations at SDZ normally appeared in evening and night, but appeared in morning at LA. The TNMHCs concentrations at the two sites were significantly influenced by the meteorological condition. The high TNMHC concentration associated with the local wind from the urban areas or trafic in upper reaches.     

Studying the City Plume of Berlin on 20 July 1998 with Three Different Modelling Approaches

In this paper we try to identify and describe the specifics of the Berlin city plume characterised by a zone of enhanced photochemical activity downwind of the urban area, where the major emissions of ozone precursors (NO_x and VOC) take place. Two Eulerian CTM systems (EURAD and REM3/CALGRID) and one Euler–Lagrangian model (LaMM5) are applied to thearea of Berlin/Brandenburg to investigate the processes involved in the evolution of the Berlin plume inherent to the models. The study focuses on 20 July 1998,the first special observation period (SOP) during BERLIOZ. The examination includes (1) the role of turbulence and transport and the role of mass flux to the surface during the evolution of the plume, (2) the import situation of the ground based measurement sites, (3)the terms of the ozone budget equation and their contribution to precursor distribution and ozone formation, (4) the substructures of the plume defined by its chemical regimes. Main results show that the complex meteorological conditions during this SOP with considerable turbulent transports demand an Euler–Lagrangian approach to determine the source receptor relationshipsfor the ground based measurement sites. These relations reveal that only a minor part (5%) of the air approaching Pabstthum and the more downwind (north-western) stations origins from Berlin and that the mutual transport between all sites was limited. The latter result afflicts the joint interpretation of data from different stations because the presumption to measure the same air mass is violated in many cases for this SOP. The CTM results reveal that the local net production of ozone within the plume was controlled by transport ad chemical processes both owning the same importance but tending to counteract each other. At this SOP far distance sources of ozone precursors originating from the Bohemian basin did not interfere the Berlin city plume although they generally have the potential to do so.     

The marine source of C2-C6 aliphatic hydrocarbons

C₂-C₆ Nonmethane hydrocarbon (NMHC) concentrations in the atmospheric boundary layer and in surface seawater were simultaneously measured during an oceanographic cruise in the intertropical Indian Ocean. NMHC were found to be mainly C₂-C₄ alkenes and C₂-C₃ alkanes. Their concentrations ranged from 1 to 30×10^–9 l/l in the seawater and 0.1 to 15 ppbv in the atmosphere. Seawater appeared to be a source because the C₂-C₆ NMHC were supersaturated with respect to the atmosphere by 2 or 3 orders of magnitude.After a selection of the pure marine atmospheric samples, performed with the help of stable and radioactive continental tracers, we found an identical composition in NMHC of surface air and seawater. This observation enabled us to establish that the gas transfer between sea and air occurred according to nonsteady state processes, and that the fluxes cannot be deduced only from atmospheric measurements. An order of magnitude value of the oceanic source for the different NMHC is however derived from the comparison of their sea water concentrations to that of propane and an independent evluation of the marine source of this last compound.     

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.     

The tropospheric distribution of carbon monoxide as observed during the Tropoz II experiment

As part of the TROPOZ II large-scale measurement campaign in January 1991 we deployed a Four Laser Airborne Infra Red (FLAIR) tunable diode laser spectrometer on board a Caravelle 116 research aircraft. We report here in situ CO measurements which were obtained with one of the four channels of the FLAIR instrument at a time resolution of either one or two minutes. The flight route of the TROPOZ II campaign followed the Atlantic coasts of North America, the Pacific and Atlantic coasts of South America and the Atlantic coasts of West Africa and Europe. A total of 48 CO vertical profiles extending from the surface to 10.5 km altitude were obtained. In the meridional direction adjacent profiles were separated by less than 10° latitude. Polewards of 30°S the CO distribution was very homogeneous with a mean mixing ratio of 55 ppbv. Between 30°S and the equator, the CO mixing ratio above 8 km altitude ranged up to 130 ppbv and was 20–60 ppbv higher than in the mid free troposhere. Three day backward trajectories for these CO rich airmasses originated over Amazonia. Earlier trace gas measurements as well as circulation studies suggested that these airmasses were of Northern Hemispheric origin and had been rapidly convected to the upper troposphere over central South America. The influence of biomass burning is clearly apparent from the measurements performed at 10°N on the African side of the Atlantic with CO mixing ratios being 100–300% higher than on the Central American side. CO mixing ratios further north ranged from 80 to 130 ppbv in the free troposphere and increased to 130–150 ppbv at lower altitudes.     

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 10³ cm^-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO₂) and methyl nitrate (CH₃ONO₂) were shown to be minor components of the total NO _y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO₂ to HOCl or Cl₂ were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.     

Diurnal cycles of formic and acetic acids in the northern part of the Guayana shield,Venezuela

Formic and acetic acids were measured in a scrub-grass savanna and in a nearby semideciduous forest. Gaseous HCOOH and CH₃COOH were collected using the mist-scrubber technique, and were determined using ion chromatography. A strong diurnal cycle was observed at both sites, with higher mixing ratios during daytime. Concentrations in the savanna were always higher than in the forest. Most of the time HCOOH/CH₃COOH ratios greater than one were recorded at the savanna site, and ratios less than one at the forest site. Boundary-layer mixing ratios in the savanna region, derived from measurements during midday, are 1.3±0.4 ppbv and 0.7±0.3 ppbv for HCOOH and CH₃COOH. Dry depositions velocities between 0.5 and 1 cm s^-1 were estimated for the savanna region. Atmospheric residence times of <3 days and >5 days were estimated for the rainy and dry season, respectively.     

Measurements of Trace Gases in the Inflow of South China Sea Background Air and Outflow of Regional Pollution at Tai O, Southern China

We present a 16-month record of ozone (O₃), carbon monoxide (CO), total reactive nitrogen (NO_y), sulphur dioxide (SO₂), methane (CH₄), C₂ – C₈ non-methane hydrocarbons (NMHCs), C₁ – C₂ halocarbons, and dimethyl sulfide (DMS) measured at a southern China coastal site. The study aimed to establish/update seasonal profiles of chemically active trace gases and pollution tracers in subtropical Asia and to characterize the composition of the `background' atmosphere over the South China Sea (SCS) and of pollution outflow from the industrialized Pearl River Delta (PRD) region and southern China. Most of the measured trace gases of anthropogenic origin exhibited a winter maximum and a summer minimum, while O₃ showed a maximum in autumn which is in contrast to the seasonal behavior of O₃ in rural eastern China and in many mid-latitude remote locations in the western Pacific. The data were segregated into two groups representing the SCS background air and the outflow of regional continental pollution (PRD plus southern China), based on CO mixing ratios and meteorological conditions. NMHCs and halocarbon data were further analyzed to examine the relationships between their variability and atmospheric lifetime and to elucidate the extent of atmospheric processing in the sampled air parcels. The trace gas variability (S) versus lifetime (τ) relationship, defined by the power law, S_lnx = Aτ^{− b}, (where X is the trace gas mixing ratio) gives a fit parameter A of 1.39 and exponent b of 0.42 for SCS air, and A of 2.86 and b of 0.31 for the regional continental air masses. An examination of ln[n-butane]/ln[ethane] versus ln[propane]/ln[ethane] indicates that their relative abundance was dominated by mixing as opposed to photochemistry in both SCS and regional outflow air masses. The very low ratios of ethyne/CO, propane/ethane and toluene/benzene suggest that the SCS air mass has undergone intense atmospheric processing since these gases were released into the atmosphere. Compared to the results from other polluted rural sites and from urban areas, the large values of these species in the outflow of PRD/southern China suggest source(s) emitting higher levels of ethyne, benzene, and toluene, relative to light alkanes. These chemical characteristics could be unique indicators of anthropogenic emissions from southern China.     

An ozone depletion event in the sub-arctic surface layer over Hudson Bay,Canada

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) program, aircraft flights during April 7–11, 2000 revealed a large area air mass capped below ∼500 m altitude over Hudson Bay, Canada in which ozone was reduced from normal levels of 30–40 ppbv to as low as 0.5 ppbv. From some of the in-situ aircraft measurements, back-trajectory calculations, the tropospheric column of BrO derived from GOME satellite measurements, and results from a regional model, we conclude that the event did not originate from triggering of reactive halogen release in the sub-Arctic region of Hudson Bay but resulted from such an event occurring at higher latitudes over the islands of the northern Canada Archipelago and nearby Arctic Ocean with subsequent transport over a distance of 1,000–1,500 km to Hudson Bay. BrO _x remained active during this transport despite considerable changes in the conditions of the underlying surface suggesting that chemical recycling during transport dominated any local halogen input from the surface. If all of the tropospheric column density of BrO is distributed uniformly within the surface layer, then the mixing ratio of BrO derived from the satellite measurements is at least a factor of 2–3 larger than derived indirectly from in situ aircraft measurements of the NO/NO₂ ratio.