Gaseous and Particulate Oxidized and Reduced Nitrogen Species in the Atmospheric Boundary Layer in Scandinavia in Spring

Observations of the concentration of several nitrogen containing compounds at five rural Scandinavian sites during March–June 1993 are reported. Total nitrate (NO ₃ ^- + HNO₃) and total ammonium (NH ₄ ⁺ + NH₃) were measured by denuder and filter pack. In general the methods agree well. At all sites the particulate fraction dominated, with the largest fraction of NO ₃ ^- and the lowest of NH ₄ ⁺ at the sites which were closest to the emission sources. The fraction of NO ₃ ^- of total nitrate increased with increasing NO₂ concentrations, indicating that the nighttime conversion of NO₂ to NO ₃ ^- is an important route of formation for NO ₃ ^- . A positive correlation was found between HNO₃ and O₃ in June at all sites, while no correlation was found early in the spring. Model calculations were made with a lagrangian boundary layer photooxidant model for the whole period, and compared to the measured concentrations. The calculated ratio between mean observed and modelled daily maximum concentrations of ozone over the measurement period were within +/–10% at all sites. The models ability to describe the daily ozone maximum concentration was satisfactory with an average deviation of 19–22% from the observed concentrations. HNO₃ was underestimated by over 50% at all sites except the one closest to the emission sources. The correlation between modelled and observed concentrations was generally best for the sites with shortest transport distance from the sources of emission.     

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.     

Carbonyls and nonmethane hydrocarbons at rural European sites from the mediterranean to the arctic

Results of regular measurements during 1992–1995 of hydrocarbons and carbonyl compounds for a number of rural European monitoring sites are presented. The measurements are part of the EMEP programme for VOC measurements in Europe. In addition, several years of regular measurements are included from the Norwegian stations Birkenes at the south coast, and Zeppelin Mountain on Spitsbergen in the Arctic. The sampling frequency has been about twice per week throughout the years, implying that a substantial amount of measurement data are available. Almost all the chemical analyses have been performed by one laboratory, the EMEP Chemical Co-ordinating Centre located at NILU, which avoids problems of intercomparison and intercalibration among different laboratories. For the measured concentrations both seasonal and geographical variations are shown and discussed. The diurnal cycles of the hydrocarbon concentrations were studied in detail at one site, where the grab samples by EMEP where compared with a parallel continuous sampler, operated by EMPA, Switzerland. Hydrocarbons linked to natural gas and fuel evaporation become well mixed into the Arctic in the winter, whereas combustion products show a latitudinal gradient. The sum of oxygenated species constitutes about 5–15% of the sum of C₂–C₅ hydrocarbons in winter. In summer they are almost equal in magnitude, consistent with an increasing oxidation of hydrocarbons.     

Mathematical modelling of the annual temperature wave based on monthly mean temperatures,and comparisons between local climate trends at seven Norwegian stations

Summary Based on observed monthly mean temperatures, it is possible to construct a simple mathematical model of the annual variation of daily mean temperature, the annual temperature wave. For periods of 15 years, the model gives a good correlation with the observed monthly values. The model may be used as a tool for the generation of daily mean temperatures for the corresponding period. It is continuous, differentiable and strictly monotonous between the unique maximum and the minimum of the curve. Consequently, climate quantities of interest for each period can be calculated by the means of simple mathematical analyses. The model was tested by reproducing values for quantities such as annual mean temperature, winter mean temperature, summer mean temperature and temperature sums. Model calculated values, fit values calculated directly from observed data well. The model was also tested by comparing results from two different but neighbouring stations. There was a good correlation between the results from the two stations. Long homogenised time series with 130 years of monthly mean temperature from seven Norwegian stations were analysed by means of the model. It was found that the Frost Free Season Length and the Growth Season Length had increased for all stations by 10–20 days/100 years in the period 1871–1990. The Summer Half-year Length, even if it was defined relative to the annual mean temperature, also increased for all stations by 4–9 days/100 years. The Hot Season Length showed positive trends as well, and for the five stations in Southern Norway, the trends were as high as 18–29 days/100 years. The Heat Sum had increased by 6–11% for southern stations and 20–22% for the northern stations. The results indicate that the level as well as the shape of the annual temperature wave changed in the period from 1871 to 1990. Some of the results for the period 1990–1999 diverge substantially from the trends, possibly indicating significant changes in the shape of the annual temperature wave in this last period.     

Nonmethane hydrocarbons in an oceanic atmosphere

C₂–C₆ Nonmethane hydrocarbons (NMHC) and radioactive continental tracers were measured during two oceanographic cruises, in June 1982 in the Mediterranean and Red Sea, and in November 1982 across the North Atlantic and South Pacific oceans. Typical concentrations in marine atmosphere are between 0.05 and 0.2 ppbv. Owing to their similar lifetimes, propane and radon-222 are found to be well correlated. This relationship establishes that propane is mainly produced over lands and enables us to estimate its continental source strength at about 60×10⁶ tons of carbon per year.Also at Université de Picardie     

A global three-dimensional model of the tropospheric sulfur cycle

The tropospheric part of the atmospheric sulfur cycle has been simulated in a global three-dimensional model. The model treats the emission, transport, chemistry, and removal processes for three sulfur components; DMS (dimethyl sulfide), SO₂ and SO₄ ^2– (sulfate). These processes are resolved using an Eulerian transport model, the MOGUNTIA model, with a horizontal resolution of 10° longitude by 10° latitude and with 10 layers in the vertical between the surface and 100 hPa. Advection takes place by climatological monthly mean winds. Transport processes occurring on smaller space and time scales are parameterized as eddy diffusion except for transport in deep convective clouds which is treated separately. The simulations are broadly consistent with observations of concentrations in air and precipitation in and over polluted regions in Europe and North America. Oxidation of DMS by OH radicals together with a global emission of 16 Tg DMS-S yr^–1 from the oceans result in DMS concentrations consistent with observations in the marine boundary layer. The average turn-over times were estimated to be 3, 1.2–1.8, and 3.2–6.1 days for DMS, SO₂, and SO₄ ^2– respectively.     

On the Budget of OH Radicals and Ozone in an Urban Plume from the Decay of C5–C8 Hydrocarbons and NOx

Simultaneous measurements of ozone and ozoneprecursors were made during a field campaign atSchauinsland in the Black Forest and in the valleynorth of Schauinsland that channels the flow ofpolluted air from the city of Freiburg to the site.From the decay of hydrocarbons and NO_x between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HO_x it is concluded that therelatively high OH concentrations (5–8 ×10⁶cm^-3) in the presence of high NO₂concentrations cannot be explained by the knownprimary sources. The budget can be closed if efficientrecycling of OH via HO₂ is assumed to occur andthat, based on the measured hydrocarbons, 2 HO₂molecules are formed for each OH radical that reactswith a hydrocarbon molecule. This assumption is inaccordance with the budget of O_x obtained from ourmeasurements and with results from earliermeasurements of alkylnitrates and peroxy radicals atSchauinsland. A possible conclusion is that the decayof precursors and production of photooxidants in urbanplumes proceeds at a faster rate than is currentlyassumed. The potential role of biogenichydrocarbons for the radical budget is alsodiscussed.     

Quantifying the water vapour feedback associated with post-Pinatubo global cooling

There is an ongoing important debate about the role of water vapour in climate change. Predictions of future climate change depend strongly on the magnitude of the water vapour feedback and until now models have almost exclusively been relied upon to quantify this feedback. In this work we employ observations of water vapour changes, together with detailed radiative calculations to estimate the water vapour feedback for the case of the Mt. Pinatubo eruption. We then compare our observed estimate with that calculated from a relatively large ensemble of simulations from a complex coupled climate model. We calculate an observed water vapour feedback parameter of –1.6 Wm^–2 K^–1, with uncertainty placing the feedback parameter between –0.9 to –2.5 Wm^–2 K^–1. The uncertain is principally from natural climate variations that contaminate the volcanic cooling. The observed estimates are consistent with that found in the climate model, with the ensemble average model feedback parameter being –2.0 Wm^–2 K^–1, with a 5–95% range of –0.4 to –3.6 Wm^–2 K^–1 (as in the case of the observations, the spread is due to an inability to separate the forced response from natural variability). However, in both the upper troposphere and Southern Hemisphere the observed model water vapour response differs markedly from the observations. The observed range represents a 40%–400% increase in the magnitude of surface temperature change when compared to a fixed water vapour response and is in good agreement with values found in other studies. Variability, both in the observed value and in the climate models feedback parameter, between different ensemble members, suggests that the long-term water vapour feedback associated with global climate change could still be a factor of 2 or 3 different than the mean observed value found here and the model water vapour feedback could be quite different from this value; although a small water vapour feedback appears unlikely. We also discuss where in the atmosphere water vapour changes have their largest effect on surface climate.     

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.     

A Long Term Study on Chemical Composition of Rainwater at Dayalbagh, a Suburban Site of Semiarid Region

Rainwater samples were collected for the monsoon period of 1988 and 1991–1996 at Dayalbagh (Agra), a suburban site situated in semiaridregion. The mean pH was 7.01 ±1.03 well above 5.6, which is the reference pH. Concentration of Ca²⁺ was observed to be highest followed by Mg²⁺, NH₄ ⁺,SO₄ ^2–, Cl^–,NO₃ ^–, Na⁺, F^– and K⁺. The ratios of SO₄ ^2– + NO₃ ^– andCa²⁺ + Mg²⁺ (TA/TC) have been considered as indicatorfor acidity. In the Agra region ratio of TA/TC is quite below 1.0 indicating alkaline nature of rainwater. The lowest value of 0.24 was observed in 1991 likely due to the lowest rain depth of the decade. The highest value of 0.54 was observed in 1996, a year with a large rain depth and increase in line (vehicular traffic) and area sources (population growth). Good correlation between Ca²⁺ and NO₃ ^–,Ca²⁺ and SO₄ ^2– andSO₄ ^2– and NO₃ ^–,indicates that wind carried dust and soil play a significant role in neutralization of precipitation acidity.     

Automated in-situ monitoring of atmospheric non-methane hydrocarbon concentrations and gradients

A fully automated system measuring C2–C6 hydrocarbon concentrations and vertical gradients was installed at Harvard Forest in Petersham, Massachusetts, using a gas chromatograph with dual flame ionization detectors and cryogenic sample preconcentration. Measurements were made simultaneously at two heights above the forest canopy at forty five minute intervals, continuously from July 1992 to the present. Data for concentration gradients were combined with CO₂ flux measured by eddy correlation to determine the rates of production of biogenic hydrocarbons by the forest.     

Long-Term Measurements of Light Hydrocarbons (C2–C5) at Schauinsland (Black Forest)

Long-term measurements of light hydrocarbons(C₂–C₅ HCs) were performed in the courseof the EUROTRAC sub-project TOR (Tropospheric Ozone Research) in thesouthern part of the Black Forest in southwest Germany. The measurementscover a time period of five years (January 1989–January 1994) and theair samples were analyzed onsite by an automated GC-system. Pronouncedannual cycles with maxima in late winter and minima in late summer wereobserved in the case of the slowly reacting hydrocarbons ethane, propane andacetylene, reflecting the fact that the seasonal variation of these speciesis photochemically driven. For the shorter lived compounds the seasonalvariations are considerably weaker, connected with a stronger scatter of theindividual measurements, which is caused by different distances to theirmain sources for different wind vectors as well as by varying sourcestrengths. From a detailed characterization of the hydrocarbon patterns theinfluence of two different sources could be distinguished. An extrapolationto photochemical age of zero and completion of our data with those from aspeciated VOC inventory yields an estimated [VOC]/NO_x sourceratio for Schauinsland of 5 [ppbC/ppb]. Comparable[VOC]/NO_x ratios are observed in automobile exhaust gasesunder low speed conditions, which points to the important role of trafficunder conditions, when freshly polluted air masses from a near-by city areadvected to the site. From an investigation of the photochemical age of theadvected air masses it becomes clear that there must exist biogenic sourcesof light olefins in the vicinity of the observatory during the vegetationperiod. For propene and the butenes we are able to estimate a lower limit oftheir contributions in terms of reactivity to the total reactivity( [HC](i) k_OH(i),i=C₂-C₅) of the measured hydrocarbons. Forlowest pollution levels in summer (acetylene <300 ppt, about 40%of the summer values) this source is found to be responsible for15–20% of the total C₂–C₅reactivity observed at Schauinsland. On the average, this source accountsfor 5–10% of the total C₂–C₅reactivity.     

Ozone production potential following convective redistribution of biomass burning emissions

The effects of deep convection on the potential for forming ozone (ozone production potential) in the free troposphere have been simulated for regions where the trace gas composition is influenced by biomass burning. Cloud dynamical and photochemical simulations based on observations in 1980 and 1985 Brazilian campaigns form the basis of a sensitivity study of the ozone production potential under differing conditions. The photochemical fate of pollutants actually entrained in a cumulus event of August 1985 during NASA/GTE/ABLE 2A (Case 1) is compared to photochemical ozone production that could have occurred if the same storm had been located closer to regions of savanna burning (Case 2) and forest burning (Case 3). In each case studied, the ozone production potential is calculated for a 24-hour period following convective redistribution of ozone precursors and compared to ozone production in the absence of convection. In all cases there is considerably more ozone formed in the middle and upper troposphere when convection has redistributed NO_x, hydrocarbons and CO compared to the case of no convection.In the August 1985 ABLE 2A event, entrainment of a layer polluted with biomass burning into a convective squall line changes the free tropospheric cloud outflow column (5–13 km) ozone production potential from net destruction to net production. If it is assumed that the same cloud dynamics occur directly over regions of savanna burning, ozone production rates in the middle and upper troposphere are much greater. Diurnally averaged ozone production following convection may reach 7 ppbv/day averaged over the layer from 5–13 km-compared to typical free tropospheric concentrations of 25–30 ppbv O₃ during nonpolluted conditions in ABLE 2A. Convection over a forested region where isoprene as well as hydrocarbons from combustion can be transported into the free troposphere leads to yet higher amounts of ozone production.     

Global NOx Production by Lightning

Lightning is thought to represent an important source of tropospheric reactive nitrogen species NO_x (NO + NO₂),but estimates of global production of NO_x by lightning varyconsiderably. We evaluate the production of NO_x by lightning using a global chemical/transport model, satellite lightning observations, and airborne NO_x measurements. Various model calculations are conducted toassess the global NO_x production rate of lightning by comparing the model calculations with airborne measurements. The results show that the simulated NO_x in the tropical middle and upper troposphere are very sensitiveto the amount and altitude of the lightning NO_x used in the model. A global lightning NO_x production of 7 Tg N yr^–1uniformly distributed in convective clouds or 3.5 Tg N yr^–1 distributedin the upper cloud regions produces good agreement between calculated and measured NO_x concentrations in the tropics.     

Tree-Ring Reconstructed Winter Precipitation and Tropical Teleconnections in Durango, Mexico

Earlywood width chronologies from Douglas-fir tree rings were used to reconstruct winter (November–March) precipitation for more than 600 years over Durango, Mexico. The tree-ring data were obtained from two sites of long-lived Douglas-fir in northern and southern Durango and the seasonal climatic precipitation data were regionally averaged from five weather stations well distributed across the state. The averaged earlywood chronology accounted for 56% of the variance in instrumental November–March precipitation 1942–1983. We validated the reconstruction against independent precipitation records. The worst winter drought of the 20th century in Durango occurred 1950–1965. However, the reconstruction indicates droughts more severe than any witnessed in the 20th century, e.g., the 1850s–1860s, and the megadrought in the mid- to late-16th century. Reconstructed winter precipitation 1540–1579 shows 33 of 40 years were dry. Persistent drought may be linked to extended La Niña episodes. The Tropical Rainfall Index (TRI) correlates well with instrumental and reconstructed winter precipitation (r = 0.49 and 0.55, respectively), reflecting the strong ENSO modulation of cool season climate over northern Mexico. The ENSO teleconnection varies through time, with TRI-reconstructed precipitation correlations ranging from 0.78 to 0.27 in five periods 1895–1993. The 1942–1983 winter observed and reconstructed Durango data correlate well with the corresponding seasonalization of the All-Mexico Rainfall Index (AMRI; r=0.68, P<0.0001 and r=0.70, P<0.001, respectively), indicating that both the observed and the reconstructed precipitation often reflect broad-scale precipitation anomalies across Mexico. New long Douglas-fir and baldcypress tree-ring chronologies are now available for central and southern Mexico near major population centers, allowing the exploration of relationships between drought, food scarcity, and social and political upheaval in Mexican history.     

Precipitation Chemistry in Semi-Arid Areas of Southern Africa: A Case Study of a Rural and an Industrial Site

Experimental data on the precipitation chemistry in the semi-arid savanna of South Africa is presented in this paper. A total of 901 rainwater samples were collected with automatic wet-only samplers at a rural site, Louis Trichardt, and at an industrial site, Amersfoort, from July 1986 to June 1999. The chemical composition of precipitation was analysed for seven inorganic and two organic ions, using ion chromatography. The most abundant ion was SO₄ ^{2 –} and a large proportion of theprecipitation is acidic, with 98% of samples at Amersfoort and 94% at LouisTrichardt having a pH below 5.6 (average pH of 4.4 and 4.9, respectively). This acidity results from a mixture of mineral and organic acids, with mineral acids being the primary contributors to the precipitation acidity in Amersfoort, while at Louis Trichardt, organic and mineral acids contribute equal amounts of acidity. It was found that the composition of rainwater is controlled by five sources: marine, terrigenous, nitrogenous, biomass burning and anthropogenic sources. The relative contributions of these sources at the two sites were calculated. Anthropogenic sources dominate at Amersfoort and biomass burning at Louis Trichardt. Most ions exhibit a seasonal pattern at Louis Trichardt, with the highest concentrations occurring during the austral spring as a result of agricultural activities and biomass combustion, while at Amersfoort it is less pronounced due to the dominance of relatively constant industrial emissions. The results are compared to observations from other African regions.     

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.     

Concentration and gas/particle partitioning of polychlorinated biphenyls (PCBs) at an industrial site at Bursa, Turkey

Gas and particle phase concentrations of atmospheric polychlorinated biphenyls (PCBs) were measured at an urban/industrial site in the city of Bursa, Turkey. PCB concentration levels were presented between July 2004 and May 2005. Average particle and gas phase concentrations of individual PCB congeners ranged from 0.08 (PCB-183) to 6.86 (PCB-49) pg m^− 3 and from 0.01 (PCB-209) to 47.2 (PCB-33) pg m^− 3, respectively. The mean concentration of total (gas + particle) PCBs varied between 24.27 and 666.21 pg m^− 3 with an average of 287.27 ± 174.80 pg m^− 3. PCB concentrations at the sampling site were higher than the concentrations reported at non-urban sites. PCBs partitioned between gas and particle phases and the partitioning was examined according to different approaches such as logK_p–logP_L^o, logK_p–logK_OA and the Junge–Pankow model. In order to present possible interactions, a correlation matrix based on PCB congeners and meteorological parameters was constructed. Application of the Clausius–Clapeyron equation yielded a low slope value indicating possible emissions from local and regional sources originating mainly from urban/industrial areas, landfill and waste incineration plant. Then, likely dry deposition fluxes were estimated depending on reported dry deposition velocity and atmospheric concentration values.     

Analysis of trace oxygenated hydrocarbons in the environment

A technique has been developed which can measure low-molecular-weight (C₂–C₅) oxygenated hydrocarbons down to concentrations of less than 10 parts per trillion (10^-12) in the atmosphere. The method uses cryogenic trapping of trace gases from the air, and two-dimensional gas chromatography (2DGC) with flame ionization and photo-ionization detectors to analyze the samples. The method has been used to make extensive measurements in the field, and it is capable of measuring all of the C₂–C₅ carbonyl compounds in clean tropospheric air. The 2DGC analytical system also makes it possible to prepare accurate, reproducible standards of the low-molecular-weight oxygenated hydrocarbons at trace levels.     

A model investigation of the impact of increases in anthropogenic NO x emissions between 1967 and 1980 on tropospheric ozone

Recent observations suggest that the abundance of ozone between 2 and 8 km in the Northern Hemisphere mid-latitudes has increased by about 12% during the period from 1970 to 1981. Earlier estimates were somewhat more conservative suggesting increases at the rate of 7% per decade since the start of regular observations in 1967. Previous photochemical model studies have indicated that tropospheric ozone concentrations would increase with increases in emissions of CO, CH₄ and NO _x . This paper presents an analysis of tropospheric ozone which suggests that a significant portion of its increase may be attributed to the increase in global anthropogenic NO _x emissions during this period while the contribution of CH₄ to the increase is quite small. Two statistical models are presented for estimating annual global anthropogenic emissions of NO _x and are used to derive the trend in the emissions for the years 1966–1980. These show steady increase in the emissions during this interval except for brief periods of leveling off after 1973 and 1978. The impact of this increase in emissions on ozone is estimated by calculations with a onedimensional (latitudinal) model which includes coupled tropospheric photochemistry and diffusive meridional transport. Steady-state photochemical calculations with prescribed NO _x emissions appropriate for 1966 and 1980 indicate an ozone increase of 8–11% in the Northern Hemisphere, a result which is compatible with the rise in ozone suggested by the observations.