Automobile Emissions of Acetonitrile: Assessment of its Contribution to the Global Source

Based on an estimated global fuel consumption of 2.57 × 10¹⁵g(C) y^–1 and the assumption thatthe fossil fuel burned in Austria is globallyrepresentative, an upper limit of 0.021 (+150%, –50%)Tg y^–1 for global CH₃CN emission dueto fossil fuel burning was obtained from the relativeenhancement of the concentrations of toluene, benzene,and acetonitrile (methyl cyanide) during strong,short-term traffic pollution. This is less than 6% ofthe total global budget of CH₃CN, which is dominatedby an emission rate of 0.8 Tg y^–1 from biomassburning.     

Estimates of global N2O emissions from cattle, pig and chicken manure, including a discussion of CH4 emissions

Humans seem to have doubled the global rate of terrestrial nitrogen fixation. Globally 50–70% (85 Tg, 1 Tg=10¹² g) of the nitrogen supplied in fertilizer (80 Tg N/a) and leguminous crops (40–80 Tg N/a) are used to feed cattle. The aim of the present study was to derive some estimates of global N₂O production from animal manure. As the parameter giving the most stable numerical basis for regional and global extrapolation we adopted the molar emission ratios of N₂O to NH₃. These ratios were measured in cattle, pig and chicken housings with different manure handling systems, in dung-heaps and in liquid manure storage tanks. Individual molar emission ratios from outside manure piles varied over two orders of magnitude, strongly dependent on the treatment of the manure. A median emission ratio of 1.6×10^-2 (n=65) was obtained in cow-sheds with slatted floors and liquid manure stored underneath and a median ratio of 24×10^-2 (n=31) was measured in a beef cattle housing with a solid manure handling system.We next extrapolated to global NH₃ emissions from those estimated for Europe, using N uptake by the animals as a scaling factor. Multiplication with observed N₂O to NH₃ ratios next provided some estimates of regional and global N₂O emissions. To account for the great variability of the emission ratios of N₂O/NH₃, we developed upper and lower case emission scenarios, based on lower and upper quartiles of measured emission ratios. The global emission from cattle and swine manure is in the range of 0.2–2.5 Tg N-N₂O/a, representing 44+-39% of the annual atmospheric accumulation rate. This N₂O emission arises from about 40 Tg N/a of cattle and pig manure stored in or at animal housings. We did not account for N₂O emissions from another 50 Tg N/a excreted by grazing cattle, goats and sheep, and application of the manure to agricultural fields. Our study makes it clear that major anthropogenic N₂O emissions may well arise from animal manure. The large uncertainty of emission ratios, which we encountered, show that much more intense research efforts are necessary to determine the factors that influence N₂O emissions from domestic animal manure both in order to derive a more reliable global estimate of N₂O release and to propose alternative waste treatment methods causing smaller N₂O releases. In our studies we found large enhancements in N₂O releases when straw was added to the manure, which is a rather common practice. In view of the ongoing discussion in Europe to re-install the traditional solid manure system (bed down cattle) for environmental and animal welfare reasons, it is noteworthy that our measurements indicate highest N₂O release from this particulary system.In a similar manner, but based on a smaller data set, we also estimated the release of CH₄ from cattle and swine manure and from liquid manure only to be about 9 Tg/year in good agreement with the estimate by the Environmental Protection Agency (1994) of 8.6+-2.6 Tg/year. A total annual methane release as high as 34 Tg/a was derived for solid and liquid cattle and pig manure from animals in housings.     

A simple model for estimating methane concentration and lifetime variations

A simple methane model is presented in which lifetime changes are expressed as a function of CH₄ concentration and emissions of NO_x CO and NMHCs. The model parameters define the relative sensitivities of lifetime to these determining factors. The parameterized model is fitted to results from five more complex atmospheric chemistry models and to 1990 IPCC concentration projections. The IPCC data and four of the five models are well fitted, implying that the models have similar relative sensitivities. However, overall sensitivities of lifetime to changes in atmospheric composition vary widely from model to model. The parameterized model is used to estimate the history of past methane emissions, lifetime changes and OH variations, with estimates of uncertainties. The pre-industrial lifetime is estimated to be 15–34% lower than today. This implies that 23–55% of past concentration changes are due to lifetime changes. Pre-industrial emissions are found to be much higher (220–330 TgCH₄/y) than the best estimate of present natural emissions (155 TgCH₄/y). The change in emissions since pre-industrial times is estimated to lie in the range 160–260 TgCH₄/y, compared with the current best guess for anthropogenic emissions of 360 TgCH₄/y. These results imply either that current estimates of anthropogenic emissions are too high and/or that there have been large changes in natural emissions. 1992 IPCC emissions scenarios are used to give projections of future concentration and lifetime changes, together with their uncertainties. For any given emissions scenario, these uncertainties are large. In terms of future radiative forcing and global-mean temperature changes over 1990–2100 they correspond to uncertainties of at least ±0.2 Wm^–2 and ± 0.1° C, respectively.     

Atmospheric methane budget in Africa

This assessment of the atmospheric methane budget for the African Continent is based on a set of experimental data obtained in tropical Africa including methane emission from various biogenic sources, and biomass burning, and methane consumption in savanna and forest soils. Emission rates from the various sources, uptake rates of soils, and complementary data from the litterature allow calculation of regional methane fluxes by means of different data bases. Biomass burning, animals and natural wetlands are the three dominant sources of methane in Africa while rice paddy fields and termites appear as minor sources. The total methane emission is estimated to be in the range 20–40 MT of CH₄ per year, methane uptake by soils being less than 2 MT per year. Net methane emission from the African continent accounts for less than 10% of global emissions from terrestrial ecosystems.     

GREENHOUSE GASES FROM DEFORESTATION IN BRAZILIAN AMAZONIA: NET COMMITTED EMISSIONS

Deforestation in Brazilian Amazonia is a significant source of greenhouse gases today and, with almost 90% of the originally forested area still uncleared, is a very large potential source of future emissions. The 1990 rate of loss of forest (13.8 × 10³ km²/year) and cerrado savanna (approximately 5 × 10³ km²/year) was responsible for releasing approximately 261 × 10⁶ metric tons of carbon (10⁶ t C) in the form of CO2, or 274–285 × 10⁶ t of CO2-equivalent C considering IPCC 1994 global warming potentials for trace gases over a 100-year horizon. These calculations consider conversion to a landscape of agriculture, productive pasture, degraded pasture, secondary forest, and regenerated forest in the proportions corresponding to the equilibrium condition implied by current land-use patterns. Emissions are expressed as net committed emissions, or the gases released over a period of years as the carbon stock in each hectare deforested approaches a new equilibrium in the landscape that replaces the original forest. For low and high trace gas scenarios, respectively, 1990 clearing produced net committed emissions (in 10⁶ t of gas) of 957–958 for CO2, 1.10–1.42 for CH₄, 28–35 for CO, 0.06–0.16 for N₂O, 0.74–0.74 for NO_x and 0.58–1.16 for non-methane hydrocarbons.     

The solubility and behaviour of acid gases in the marine aerosol

The following Henry's law constants (K _H/mol²kg^-2atm^-1) for HNO₃ and the hydrohalic acids have been evaluated from available partial pressure and other thermodynamic data from 0°–40°C, 1 atm total pressure: HNO ₃ , 40°C–5.85×10⁵; 30°C–1.50×10⁶; 25°C–2.45×10⁶; 20°C–4.04×10⁶; 10°C–1.15×10⁷; 0°C–3.41×10⁷. HF, 40°C–3.2; 30°C–6.6; 25°C–9.61; 20°C–14.0; 10°C–32.0; 0°C–76. HCl, 40°C–4.66×10⁵; 30°C–1.23×10⁶; 25°C–2.04×10⁶; 20°C–3.37×10⁶; 10°C–9.71×10⁶; 0°C–2.95×10⁷. HBr, 40°C–2.5×10⁸; 30°C–7.5×10⁸; 25°C–1.32×10⁹; 20°C–2.37×10⁹; 10°C–8.10×10⁹; 0°C–3.0×10¹⁰. HI, 40°C–5.2×10⁸; 30°C–1.5×10⁹; 25°C–2.5×10⁹; 20°C–4.5×10⁹; 10°C–1.5×10¹⁰; 0°C–5.0×10¹⁰. Simple equilibrium models suggest that HNO₃, CH₃SO₃H and other acids up to 10x less soluble than HCl displace it from marine seasalt aerosols. HF is displaced preferentially to HCl by dissolved acidity at all relative humidities greater than about 80%, and should be entirely depleted in aged marine aerosols.     

Field study of the emissions of methyl chloride and other halocarbons from biomass burning in Western Africa

A field study of trace gas emissions from biomass burning in Equatorial Africa gave methyl chloride emission ratios of 4.3×10^–5±0.8×10^–5 mol CH₃Cl/mol CO₂. Based on the global emission rates for CO₂ from biomass burning we estimate a range of 226–904×10⁹ g/y as global emission rate with a best estimate of 515×10⁹ g/y. This is somewhat lower than a previous estimate which has been based on laboratory studies. Nevertheless, our emission rate estimates correspond to 10–40% of the global turnover of methyl chloride and thus support the importance of biomass burning as methyl chloride source. The emission ratios for other halocarbons (CH₂Cl₂, CHCl₃, CCl₄, CH₃CCl₃, C₂HCl₃, C₂Cl₄, F-113) are lower. In general there seems to be a substantial decrease with increasing complexity of the compounds and number of halogen atoms. For dichloromethane biomass burning still contributes significantly to the total global budget and in the Southern Hemisphere biomass burning is probably the most important source for atmospheric dichloromethane. For the global budgets of other halocarbons biomass burning is of very limited relevance.     

Seasonal Variations of CH_4 Emissions in the Yangtze River Delta Region of China Are Driven by Agricultural Activities

Developed regions of the world represent a major atmospheric methane(CH_4) source, but these regional emissions remain poorly constrained. The Yangtze River Delta(YRD) region of China is densely populated(about 16% of China's total population) and consists of large anthropogenic and natural CH_4 sources. Here, atmospheric CH_4 concentrations measured at a 70-m tall tower in the YRD are combined with a scale factor Bayesian inverse(SFBI) modeling approach to constrain seasonal variations in CH_4 emissions. Results indicate that in 2018 agricultural soils(AGS, rice production) were the main driver of seasonal variability in atmospheric CH_4 concentration. There was an underestimation of emissions from AGS in the a priori inventories(EDGAR—Emissions Database for Global Atmospheric Research v432 or v50), especially during the growing seasons. Posteriori CH_4 emissions from AGS accounted for 39%(4.58 Tg, EDGAR v432) to 47%(5.21 Tg, EDGAR v50) of the total CH_4 emissions. The posteriori natural emissions(including wetlands and water bodies) were1.21 Tg and 1.06 Tg, accounting for 10.1%(EDGAR v432) and 9.5%(EDGAR v50) of total emissions in the YRD in2018. Results show that the dominant factor for seasonal variations in atmospheric concentration in the YRD was AGS,followed by natural sources. In summer, AGS contributed 42%(EDGAR v432) to 64%(EDGAR v50) of the CH_4 concentration enhancement while natural sources only contributed about 10%(EDGAR v50) to 15%(EDGAR v432). In addition, the newer version of the EDGAR product(EDGAR v50) provided more reasonable seasonal distribution of CH_4 emissions from rice cultivation than the old version(EDGAR v432).     

Application of stable isotope analysis for improved understanding of the methane budget: comparison of TROICA measurements with TM3 model simulations

Presented is a detailed comparison of CH₄ and δ¹³C–CH₄ measurements with simulations of the global transport model TM3. Experimental data were obtained during campaigns along the Trans-Siberian railroad in the framework of the TROICA project. Two summer (1999 and 2001) and one spring (2003) expeditions are evaluated. Model simulations include sensitivity tests to further investigate the isotopic composition of natural gas and emissions from Siberian wetlands. Comparison of the average mixing ratio of methane and its isotopic composition (δ¹³C) has been performed for different geographic zones, including the European part of Russia, Western Siberia and Central Siberia. Simulations are in reasonable agreement with the measurements for the European part of Russia and confirm a high contribution of natural gas to the observed methane levels. An increase of emission from bogs shifts the simulated methane isotopic composition closer to the observations. The relative importance of the Western Siberia emissions in current inventories is underestimated in comparison with other wetland regions in the former USSR. Simulated average mixing ratios are in a good agreement with the observations in Central Siberia, while ¹³C(CH₄) values tend to be higher than measured in all considered scenarios. These results point to a bias in the modeled source mixture over Russia, which could be repaired by shifting emissions from isotopically heavy methane sources (e.g. coal, oil or biomass burning) to light sources (e.g. wetlands, ruminants, waste treatment). Alternatively, the average isotopic signature of Siberian wetlands may be lighter than expected.     

Methane emission from rice paddies

Methane release rates from rice paddies have been measured in Andalusia, Spain, during almost a complete vegetation period in 1982 using the static box system. The release rates ranged between 2 and 14 mg/m²/h and exhibited a strong seasonal variation with low values during the tillering stage and shortly before harvest, while maximum values were observed at the end of the flowering stage. The CH₄ release rate, averaged over the complete vegetation period, accounted for 4 mg/m²/h which results in a worldwide CH₄ emission from rice paddies of 35–59×10¹² g/yr if we assume that the observed CH₄ release rates are representative of global conditions. The CH₄ release rates showed diurnal variations with higher values late in the afternoon which were most likely caused by temperature variations within the upper layers of the paddy soils. Approximately 95% of the CH₄ emitted into the atmosphere by rice paddies was due to transport through the rice plants. Transport by bubbles or diffusion through the paddy water was of minor importance. Incubation experiments showed that CH₄ was neither produced nor consumed in the paddy water. The relase of CH₄ from rice paddies caused a diurnal variation of CH₄ in ambient air within the rice-growing area with maximum values of up to 2.3 ppmv during the early morning, compared to average daytime values of 1.75 ppmv.     

Domestic Combustion of Biomass Fuels in Developing Countries: A Major Source of Atmospheric Pollutants

Biomass burning has important impacts on atmospheric chemistry and climate. Fires in tropical forests and savannas release large quantities of trace gases and particulate matter. Combustion of biofuels for cooking and heating constitutes a less spectacular but similarly widespread biomass burning activity. To provide the groundwork for a quantification of this source, we determined in rural Zimbabwe the emissions of CO₂, CO, and NO from more than 100 domestic fires fueled by wood, agricultural residues, and dung. The results indicate that, compared to open savanna fires, emissions from domestic fires are shifted towards products of incomplete combustion. A tentative global analysis shows that the source strength of domestic biomass burning is on the order of 1500 Tg CO₂–C yr^–1, 140 Tg CO–C yr^–1, and 2.5 Tg NO–N yr^–1. This represents contributions of about 7 to 20% to the global budget of these gases.     

Global Warming and Tropical Land-Use Change: Greenhouse Gas Emissions from Biomass Burning, Decomposition and Soils in Forest Conversion, Shifting Cultivation and Secondary Vegetation

Tropical forest conversion, shiftingcultivation and clearing of secondary vegetation makesignificant contributions to global emissions ofgreenhouse gases today, and have the potential forlarge additional emissions in future decades. Globally, an estimated 3.1×10⁹ t of biomasscarbon of these types is exposed to burning annually,of which 1.1×10⁹ t is emitted to the atmospherethrough combustion and 49×10⁶ t is converted tocharcoal (including 26–31×10⁶ t C of blackcarbon). The amount of biomass exposed to burningincludes aboveground remains that failed to burn ordecompose from clearing in previous years, andtherefore exceeds the 1.9×10⁹ t of abovegroundbiomass carbon cleared on average each year. Above-and belowground carbon emitted annually throughdecomposition processes totals 2.1×10⁹ t C. Atotal gross emission (including decomposition ofunburned aboveground biomass and of belowgroundbiomass) of 3.41×10⁹ t C year^-1 resultsfrom clearing primary (nonfallow) and secondary(fallow) vegetation in the tropics. Adjustment fortrace gas emissions using IPCC Second AssessmentReport 100-year integration global warming potentialsmakes this equivalent to 3.39×10⁹ t ofCO₂-equivalent carbon under a low trace gasscenario and 3.83×10⁹ t under a high trace gasscenario. Of these totals, 1.06×10⁹ t (31%)is the result of biomass burning under the low tracegas scenario and 1.50×10⁹ t (39%) under thehigh trace gas scenario. The net emissions from allclearing of natural vegetation and of secondaryforests (including both biomass and soil fluxes) is2.0×10⁹ t C, equivalent to 2.0–2.4×10⁹ t of CO₂-equivalent carbon. Adding emissions of0.4×10⁹ t C from land-use category changesother than deforestation brings the total for land-usechange (not considering uptake of intact forest,recurrent burning of savannas or fires in intactforests) to 2.4×10⁹ t C, equivalent to 2.4–2.9×10⁹ t of CO₂-equivalent carbon. The totalnet emission of carbon from the tropical land usesconsidered here (2.4×10⁹ t C year^-1)calculated for the 1981–1990 period is 50% higherthan the 1.6×10⁹ t C year^-1 value used by the Intergovernmental Panel on Climate Change. The inferred (= `missing') sink in the global carbonbudget is larger than previously thought. However,about half of the additional source suggested here maybe offset by a possible sink in uptake by Amazonianforests. Both alterations indicate that continueddeforestation would produce greater impact on globalcarbon emissions. The total net emission of carboncalculated here indicates a major global warmingimpact from tropical land uses, equivalent toapproximately 29% of the total anthropogenic emissionfrom fossil fuels and land-use change.     

Sink Potential of Canadian Agricultural Soils

Net greenhouse gas (GHG) emissions from Canadian crop and livestock production were estimated for 1990, 1996 and 2001 and projected to 2008. Net emissions were also estimated for three scenarios (low (L), medium (M) and high (H)) of adoption of sink enhancing practices above the projected 2008 level. Carbon sequestration estimates were based on four sink-enhancing activities: conversion from conventional to zero tillage (ZT), reduced frequency of summerfallow (SF), the conversion of cropland to permanent cover crops (PC), and improved grazing land management (GM). GHG emissions were estimated with the Canadian Economic and Emissions Model for Agriculture (CEEMA). CEEMA estimates levels of production activities within the Canadian agriculture sector and calculates the emissions and removals associated with those levels of activities. The estimates indicate a decline in net emissions from 54 Tg CO₂–Eq yr^–1 in1990 to 52 Tg CO₂–Eq yr^–1 in 2008. Adoption of thesink-enhancing practices above the level projected for 2008 resulted in further declines in emissions to 48 Tg CO₂–Eq yr^–1 (L), 42 TgCO₂–Eq yr^–1 (M) or 36 Tg CO₂–Eq yr^–1 (H). Among thesink-enhancing practices, the conversion from conventional tillage to ZT provided the largest C sequestration potential and net reduction in GHG emissions among the scenarios. Although rates of C sequestration were generally higher for conversion of cropland to PC and adoption of improved GM, those scenarios involved smaller areas of land and therefore less C sequestration. Also, increased areas of PC were associated with an increase in livestock numbers and CH₄ and N₂O emissions from enteric fermentation andmanure, which partially offset the carbon sink. The CEEMA estimates indicate that soil C sinks are a viable option for achieving the UNFCCC objective of protecting and enhancing GHG sinks and reservoirs as a means of reducing GHG emissions (UNFCCC, 1992).     

CH4 emission from various rice fields in P.R. China

Summary The CH₄ emission rates from Chinese rice fields have been measured in five typical areas representing all of the five major rice culture regions in People's Republic of China (P.R. China). Four types of diurnal variations (afternoon peak, night peak, afternoon-night double peaks and random pattern) of CH₄ emission rates have been found. The first pattern was normally found in clear weather, the second and the third types were only found occasionally in particular place, while the fourth were found in cloudy or rainy weather. Due to the irregular pattern of the methane production observed in the morning-afternoon comparison experiment, the transport pathway influenced by certain factors, may be the major factor governing the diurnal variation of CH₄ emission. Seasonal variation patterns of CH₄ emission differ slightly with different field locations, where climate system, cropping system and other factors are different. Two and three emission peaks were generally found during single and early rice vegetation periods, with the peak magnitude and time of appearance differing to small degree in individual sites. A decreasing trend of seasonal variation was always observed in late rice season. A combination of seasonal change of transport efficiency and that of CH₄ production rate in the paddy soil explains well the CH₄ emission. The role of rice plant in transporting CH₄ varied over a large range in different rice growing stages. The reasons for internnual changes of CH₄ flux are not yet clear.Great spatial variation of the CH₄ emission has been found, which can be attributed to the differences in soil type and soil properties, local climate condition, rice species, fertilizer and water treatment. Experiments showed that while the application of some mineral fertilizers will reduce the CH₄ emission and CH₄ production in the soil, the application of organic manure will enhance CH₄ emission and CH₄ production in the soil. Any measures which can get off easily decomposed carbon from organic manure may reduce C supply for CH₄ production, and hence reduce CH₄ emission. Fermented sludges from biogas generators and farmyard-stored manure seem to be promising. In some parts of China, separate application of the organic and mineral manure instead of mixed application could be another option. Frequent Scientific drainage and ridge cultivation, which are often used water management techniques in Chinese rice agriculture, have been proved in the experiments to be a very efficient mitigation measures to reduce CH₄ emission from rice fields.By summarizing the present available data, China's rice fields contribute about 13.3 Tg yr^–1 (11.4–15.2) CH₄ to the atmosphere. The total methane emission from global rice fields can be estimated 33–60 Tg yr^–1, much less than the estimates made before.If we extrapolate the measured data in China with a consideration of measured data in other Asian country, the total global emission of CH₄ from rice fields are estimated to be about 35–60 Tg yr^–1 With 2 Figures     

A determination of the CH4, NO x and CO2 emissions from the Prudhoe Bay,Alaska oil development

In this paper we quantify the CH₄, CO₂ and NO _x emissions during routine operations at a major oil and gas production facility, Prudhoe Bay, Alaska, using the concentrations of combustion by products measured at the NOAA-CMDL observatory at Barrow, Alaska and fuel consumption data from Prudhoe Bay. During the 1989 and 1990 measurement campaigns, 10 periods (called events) were unambiguously identified where surface winds carry the Prudhoe Bay emissions to Barrow (approximately 300 km). The events ranged in duration from 8–48 h and bring ambient air masses containing substantially elevated concentrations of CH₄, CO₂ and NO _y to Barrow. Using the slope of the observed CH₄ vs CO₂ concentrations during the events and the CO₂ emissions based on reported fuel consumption data, we calculate annual CH₄ emissions of (24+/–8)×10³ metric tons from the facility. In a similar manner, the annual NO _x emissions are calculated to be (12+/–4)×10³ metric tons, which is in agreement with an independently determined value. The calculated CH₄ emissions represent the amount released during routine operations including leakage. However this quantity would not include CH₄ released during non-routine operations, such as from venting or gas flaring.     

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.     

Fourier transform infrared studies of the reaction of Cl atoms with PAN,PPN, CH3OOH,HCOOH, CH3COCH3 and CH3COC2H5 at 295±2 K

The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with peroxyacetylnitrate (PAN), peroxypropionylnitrate (PPN), methylhydroperoxide, formic acid, acetone and butanone. Decay rates of these organic species were measured relative to one or more of the following reference compounds; ethene, ethane, chloroethane, chloromethane, and methane. Using rate constants of 9.29×10^–11, 5.7×10^–11, 8.04×10^–12, 4.9×10^–13, and 1.0×10^–13 cm³ molecule^–1 sec^–1 for the reaction of Cl atoms with ethene, ethane, chloroethane, chloromethane, and methane respectively, the following rate constants were derived, in units of cm³ molecule^–1 s^–1: PAN, <7×10^–15; PPN, (1.14±0.12)×10^–12; HCOOH, (2.00±0.25)×10^–13; CH₃OOH, (5.70±0.23)×10^–11; CH₃COCH₃, (2.37±0.12)×10^–12; and CH₃COC₂H₅, (4.13±0.57)×10^–11. Quoted errors represent 2 and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295±2 K and 700 torr total pressure of nitrogen or synthetic air. The results are discussed with respect to the previous literature data and to the modelling of nonmethane hydrocarbon oxidation in the atmosphere.In recent discussions with Dr. R. A. Cox of Harwell Laboratory, UKAEA, we learnt of a preliminary value for the rate constant of the reaction of Cl with acetone of (2.5±1.0)×10^–12 cm³ molecule^–1 sec^–1 measured by R. A. Cox, M. E. Jenkin, and G. D. Hayman using molecular modulation techniques. This value is in good agreement with our results.     

Kinetics of the Gas-Phase Reactions of OH Radicals, NO3 Radicals and O3 with Three C7-Carbonyls Formed From The Atmospheric Reactions of Myrcene, Ocimene and Terpinolene

Rate constants for the gas-phase reactions of OH radicals, NO₃ radicals and O₃ with the C₇-carbonyl compounds 4-methylenehex-5-enal [CH₂=CHC(=CH₂)CH₂CH₂CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH₂=CHC(CH₃)=CHCH₂CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm³ molecule^–1 s^–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10^–10, (4.75 ± 0.35) × 10^–13 and (1.46 ± 0.12) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10^–10, (2.17 ± 0.30) × 10^–12, and (4.13 ± 0.81) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10^–10, (1.75 ± 0.27) × 10^–12, and (5.36 ± 0.28) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10^–10, (1.81 ± 0.35) × 10^–12, and (6.98 ± 0.40) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO₃ radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.     

Tropospheric methane in the mid-latitudes of the Southern Hemisphere

Results of more than 800 new measurements of methane (CH₄) concentrations in the Southern Hemisphere troposphere (34–41° S, 130–150° E) are reported. These were obtained between September 1980 and March 1983 from the surface at Cape Grim, Tasmania, through the middle (3.5–5.5 km) to the upper troposphere (7–10 km). The concentration of CH₄ increased throughout the entire troposphere over the measurement period, adding further support to the view that CH₄ concentrations are currently increasing on a global scale. For data averaged vertically through the troposphere the rate of increase found was 20 ppbv/yr or 1.3%/yr at December 1981. In the surface CH₄ data a seasonal cycle with a peak to peak amplitude of approximately 28 ppbv is seen, with the minimum concentration occurring in March and the maximum in September–October. A cycle with the same phase as that seen at the surface, but with a significantly decreased amplitude, is apparent in the mid troposphere but no cycle is detected in the upper tropospheric data. The phase and amplitude of the cycle are qualitatively in agreement with the concept that the major sink for methane is oxidation by hydroxyl radicals. Also presented is evidence of a positive vertical gradient in methane, with a suggestion that the magnitude of this gradient has changed over the period of measurements.     

Correlations among combustion effluent species at Barrow,Alaska: Aerosol black carbon,carbon dioxide,and methane

As part of the second Arctic Gas and Aerosol Sampling Program (AGASP II) continuous measurements of atmospheric aerosol black carbon (BC) were made at the NOAA/GMCC observatory at Barrow, Alaska (71°19N, 156°36W) during the period March 21–April 22, 1986. Black carbon is produced only by incomplete combustion of carbonaceous materials and so is a particularly useful atmospheric indicator of anthropogenic activities. The BC data have been analyzed together with the concurrent measurements of carbon dioxide (CO₂), methane (CH₄), and condensation nuclei (CN) that are routinely made at the observatory. All four species showed elevated and highly variable concentrations due to local human activities, principally in the township of Barrow, 7 km to the southwest, and at the DEW Line radar installation 1 km to the northwest. We distinguish between those periods of the record that are affected by local activities and those that are not, on the basis of the short-term (periods of up to 1 hour) variability of the continuous CO₂ and CN records, with large short-term variabilities indicating local sources. We identified seven periods of time (events) with durations ranging from 13 to 37 hours when the BC, CO₂, and CH₄ concentrations changed smoothly over time, were highly correlated with each other, and were not influenced by local activities. These events had BC/CO₂ ratios in the range (50–103)×10^–6. These ratios are dimensionless since we convert the CO₂ concentrations to units of ng m^–3 of carbon. Such values of BC/CO₂ are characteristic of the combustion effluent from large installations burning heavy fuel oil or coal, automobiles, and domestic-scale natural gas usage. We conclude that these events are indicative of air masses that have been polluted with combustion emissions in a distant location and then transported to the Arctic. In the absence of species-selective loss mechanisms, these air masses will maintain their combustion effluent signatures during the transport. The BC/CO₂ ratios found for the local combustion activities are consistent with those expected from known combustion processes.