Seasonal carbon dioxide balance and respiration of a high-arctic fen ecosystem in NE-Greenland

Summary  Turbulent fluxes of CO₂ were continuously measured by eddy correlation for three months in 1997 over a gramineous fen in a high-arctic environment at Zackenberg (74°28′12″N, 20°34′23″W) in NE-Greenland. The measurements started on 1 June, when there was still a 1–2 m cover of dry snow, and ended 26 August at a time that corresponds to late autumn at this high-arctic site. During the 20-day period with snow cover, fluxes of CO₂ to the atmosphere were small, typically 0.005 mg CO₂ m⁻² s⁻¹ (0.41 g CO₂ m⁻² d⁻¹), wheres during the thawed period, the fluxes displayed a clear diurnal variation. During the snow-free period, before the onset of vegetation growth, fluxes of CO₂ to the atmosphere were typically 0.1 mg CO₂ m⁻² s⁻¹ in the afternoon, and daily sums reached values up to almost 9 g CO₂ m⁻² d⁻¹. After 4 July, downward fluxes of CO₂ increased, and on sunny days in the middle of the growing season, the net ecosystem exchange rates attained typical values of about −0.23 mg m⁻² s⁻¹ at midday and max values of daily sums of −12 g CO₂ m⁻² d⁻¹. Throughout the measured period the fen ecosystem acted as a net-sink of 130 g CO₂ m⁻². Modelling the ecosystem respiration during the season corresponded well with eddy correlation and chamber measurements. On the basis of the eddy correlation data and the predicted respiration effluxes, an estimate of the annual CO₂ balance the calender year 1997 was calculated to be a net-sink of 20 g CO₂ m⁻² yr⁻¹. Received October 6, 1999 Revised May 2, 2000     

Temperature and snow-melt controls on interannual variability in carbon exchange in the high Arctic

Summary Net Ecosystem CO₂ Exchange (NEE) was studied during the summer season (June–August) at a high Arctic heath ecosystem for 5 years in Zackenberg, NE Greenland. Integrated over the 80 day summer season, the heath is presently a sink ranging from −1.4 g C m⁻² in 1997 to −23.3 g C m⁻² in 2003. The results indicate that photosynthesis might be more variable than ecosystem respiration on the seasonal timescale. The years focused on in this paper differ climatically, which is reflected in the measured fluxes. The environmental conditions during the five years strongly indicated that time of snow-melt and air temperature during the growing season are closely related to the interannual variation in the measured fluxes of CO₂ at the heath. Our estimates suggest that net ecosystem CO₂ uptake is enhanced by 0.16 g C m⁻² per increase in growing degree-days during the period of growth. This study emphasises that increased summer time air temperatures are favourable for this particular ecosystem in terms of carbon accumulation.     

Impacts of future Indian greenhouse gas emission scenarios on projected climate change parameters deduced from MAGICC model

The MAGICC (Model for the Assessment of Greenhouse gas Induced Climate Change) model simulation has been carried out for the 2000–2100 period to investigate the impacts of future Indian greenhouse gas emission scenarios on the atmospheric concentrations of carbon dioxide, methane and nitrous oxide besides other parameters like radiative forcing and temperature. For this purpose, the default global GHG (Greenhouse Gases) inventory was modified by incorporation of Indian GHG emission inventories which have been developed using three different approaches namely (a) Business-As-Usual (BAU) approach, (b) Best Case Scenario (BCS) approach and (c) Economy approach (involving the country’s GDP). The model outputs obtained using these modified GHG inventories are compared with various default model scenarios such as A1B, A2, B1, B2 scenarios of AIM (Asia-Pacific Integrated Model) and P50 scenario (median of 35 scenarios given in MAGICC). The differences in the range of output values for the default case scenarios (i.e., using the GHG inventories built into the model) vis-à-vis modified approach which incorporated India-specific emission inventories for AIM and P50 are quite appreciable for most of the modeled parameters. A reduction of 7% and 9% in global carbon dioxide (CO₂) emissions has been observed respectively for the years 2050 and 2100. Global methane (CH₄) and global nitrous oxide (N₂O) emissions indicate a reduction of 13% and 15% respectively for 2100. Correspondingly, global concentrations of CO₂, CH₄ and N₂O are estimated to reduce by about 4%, 4% and 1% respectively. Radiative forcing of CO₂, CH₄ and N₂O indicate reductions of 6%, 14% and 4% respectively for the year 2100. Global annual mean temperature change (incorporating aerosol effects) gets reduced by 4% in 2100. Global annual mean temperature change reduces by 5% in 2100 when aerosol effects have been excluded. In addition to the above, the Indian contributions in global CO₂, CH₄ and N₂O emissions have also been assessed by India Excluded (IE) scenario. Indian contribution in global CO₂ emissions was observed in the range of 10%–26%, 6%–36% and 10%–38% respectively for BCS, Economy and BAU approaches, for the years 2020, 2050 and 2100 for P50, A1B-AIM, A2-AIM, B1-AIM & B2-AIM scenarios. CH₄ and N₂O emissions indicate about 4%–10% and 2%–3% contributions respectively in the global CH₄ and N₂O emissions for the years 2020, 2050 and 2100. These Indian GHG emissions have significant influence on global GHG concentrations and consequently on climate parameters like RF and ∆T. The study reflects not only the importance of Indian emissions in the global context but also underlines the need of incorporation of country specific GHG emissions in modeling to reduce uncertainties in simulation of climate change parameters.     

Atmospheric inorganic nitrogen in marine aerosol and precipitation and its deposition to the North and South Pacific Oceans

Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH₄⁺ and ~32% NO₃^– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH₄⁺ and NO₃⁻ in rainwater ranged from 1.7–55 μmol L⁻¹ and 0.16–18 μmol L⁻¹, respectively, accounting for ~87% by NH₄⁺ and ~13% by NO₃⁻ of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH₄⁺ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH₄⁺ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH₃) by marine biological activity from the ocean could become a significant source of NH₄⁺ over the South Pacific. While NO₃⁻ was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH₄⁺ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m⁻² d⁻¹, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.     

Rain-aerosol coupling in the tropical atmosphere of Southeast Asia: distribution and scavenging ratios of major ionic species

Both aerosol and rainwater samples were collected and analyzed for ionic species at a coastal site in Southeast Asia over a period of 9 months (January–September 2006) covering different monsoons. In general, the occurrence and distribution of ionic species showed a distinct seasonal variation in response to changes in air mass origins. Real-time physical characterization of aerosol particles during rain events showed changes in particle number distributions which were used to assess particle removal processes associated with precipitation, or scavenging. The mean scavenging coefficients for particles in the range 10–500 nm and 500–10 μm were 7.0 × 10⁻⁵ ± 2.8 × 10⁻⁵ s⁻¹ and 1.9 × 10⁻⁴ ± 1.6 × 10⁻⁵ s⁻¹, respectively. A critical analysis of the scavenging coefficients obtained from this study suggested that the wet removal of aerosol particles was greatly influenced by rain intensity, and was particle size-dependent as well. The scavenging ratios, another parameter used to characterize particle removal processes by precipitation, for NH₄ ⁺, Cl⁻, SO₄ ²⁻, and NO₃ ⁻ were found to be higher than those of Na⁺, K⁺, and Ca²⁺ of oceanic and crustal origins. This enrichment implied that gaseous species NH₃, HCl, and HNO₃ could also be washed out readily. These additional sources of ions in precipitation presumably counter-balanced the dilution effect caused by high total precipitation volume in the marine and tropical area.     

Assessment of changes in methane emissions from marsh ecosystems of northern Eurasia in the 21st century using regional climate model results

Changes in methane emissions into the atmosphere from terrestrial ecosystems are assessed with models for the European and Asian parts of Russia using the model unit of a methane cycle and calculations with a regional climate model. The calculations were performed for the present-day base period (1991–2000), for the middle (2041–2050), and late (2091–2100) 21st century using the SRES A2 anthropogenic emission scenario. The average emissions for the base period were equal to 8 Mt CH₄/year for the European part of Russia and 10 Mt CH₄/year for the Asian part. By the middle of the 21st century, they increased up to 11 and 13 Mt CH₄/year, and by the late 21st century, up to 14 and 17 Mt CH₄/year. These tendencies are associated with the increased warm period of the soil and dependence of the integral methane production on temperature. It is predicted that the maximum depth of freezing will lessen in the southern regions of the European and Asian parts of Russia by the late 21st century.     

Waves to the lee of a meso-scale elliptic orographic barrier

Summary ?The paper considers a meso-scale, adiabatic, inviscid and Boussisnesq flow of a stably stratified fluid over a three-dimensional (3-D) meso-scale orographic barrier with elliptic contour, with special reference to a part of the Western ghats mountain along west coast of India and on the Khasi-Jayantia hill in the northeast India. The airstream characteristics are simplified by assuming that the upstream wind velocity (U) and buoyancy frequency (N) are constant with height. Solutions for perturbation vertical velocity (w′) and streamline displacement (η′) are expressed in terms of double integrals. These integrals cannot be evaluated exactly, hence they have been approximated by asymptotic expansion method. Side by side solutions using numerical method have also been obtained. The results of the study indicate that the updraft regions in the asymptotic solution are crescent shaped, symmetrical about the axis y = 0, tilting upwind and spreading laterally with height. The study also shows that in both asymptotic solution and numerical solution w′ and η′ fall off down wind of the barrier in the central plane (y = 0), further more in the asymptotic solution w′ and η′ fall off as x ⁻¹. The study also indicates that the discrete updraft regions obtained in the numerical solution, when joined, take a crescent shape. Received November 26, 2001; accepted February 27, 2002     

Effects of Irrigation on Nitrous Oxide, Methane and Carbon Dioxide Fluxes in an Inner Mongolian Steppe

Increased precipitation during the vegetation periods was observed in and further predicted for Inner Mongolia. The changes in the associated soil moisture may affect the biosphere-atmosphere exchange of greenhouse gases. Therefore, we set up an irrigation experiment with one watered （W） and one unwatered plot （UW） at a winter-grazed Leymus chinensis-steppe site in the Xilin River catchment, Inner Mongolia. UW only received the natural precipitation of 2005 （129 mm）, whereas W was additionally watered after the precipitation data of 1998 （in total 427 mm）. In the 3-hour resolution, we determined nitrous oxide （N20）, methane （CH4） and carbon dioxide （CO2） fluxes at both plots between May and September 2005, using a fully automated, chamber-based measuring system. N20 fluxes in the steppe were very low, with mean emissions （±s.e.） of 0.9-4-0.5 and 0.7-4-0.5 μg N m^-2 h^-1 at W and UW, respectively. The steppe soil always served as a CH4 sink, with mean fluxes of -24.1-4-3.9 and -31.1-4- 5.3 μg C m^-2 h^-1 at W and UW. Nighttime mean CO2 emissions were 82.6±8.7 and 26.3±1.7 mg C m^-2 h^-1 at W and UW, respectively, coinciding with an almost doubled aboveground plant biomass at W. Our results indicate that the ecosystem CO2 respiration responded sensitively to increased water input during the vegetation period, whereas the effects on CH4 and N2O fluxes were weak, most likely due to the high evapotranspiration and the lack of substrate for N2O producing processes. Based on our results, we hypothesize that with the gradual increase of summertime precipitation in Inner Mongolia, ecosystem CO2 respiration will be enhanced and CH4 uptake by the steppe soils will be lightly inhibited.     

Atmospheric CO along the Trans-Siberian Railroad and River Ob: source identification using isotope analysis

The concentration, radiocarbon (¹⁴C) and stable isotope (¹³C and ¹⁸O) content of CO have been determined in air samples collected across Russia (about 8,500 km) and along the Ob river during the summer of 1999 to study the CO sources and sinks. An instrumented carriage on the Trans-Siberian railway and a boat on the river Ob were used as atmospheric measurement platforms. In general, CO mixing ratios, CO stable isotope ratios, as well as the abundances of ¹⁴CO over West Siberia were similar to those found at remote northern hemispheric baseline monitoring stations. Identified sources of CO along the Ob appear to be connected to methane oxidation based on an inferred δ¹³C_source = −36.8 ± 0.6‰, while the value for δ¹⁸O_source = 9.0 ± 1.6‰ identifies it as burning. Thus flaring in the oil and gas production can be supposed to be a source. The extreme ¹³C depletion and concomitant ¹⁸O enrichment for two of the boat samples unambiguously indicates contamination by CO from combustion of natural gas (inferred values δ¹³C_source = −40.3‰ and δ¹⁸O_source = 17.5‰). For these two samples, that have strongly elevated ¹⁴CO concentrations, the industrial area near Tomsk is identified as a source area using meteorological calculations. Along the Trans-Siberian Railroad background CO was to various degrees contaminated with CO from methane combustion (δ¹³C_source = −35.7 ± 6.2‰ and δ¹⁸O_source = 10.3 ± 1.8‰). The impact of industrial burning was discernable in the vicinity of Perm-Kungur.     

Laboratory measurements of the <Superscript>12</Superscript>C/<Superscript>13</Superscript>C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k ₁₂/k ₁₃, are greater than unity or normal KIEs. The KIEs, reported in per mil according to ^Cl ɛ = (k ₁₂/k ₁₃−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed.     

The Summer Surface Energy Balance of the High Antarctic Plateau

The summertime surface energy balance (SEB) at Kohnen station, situated on the high Antarctic plateau (75°00′ S, 0°04′ E, 2892m above sea level) is presented for the period of 8 January to 9 February 2002. Shortwave and longwave radiation fluxes were measured directly; the former was corrected for problems associated with the cosine response of the instrument. Sensible and latent heat fluxes were calculated using the bulk method, and eddy-correlation measurements and the modified Bowen ratio method were used to verify these calculated fluxes. The calculated sub-surface heat flux was checked by comparing calculated to measured snow temperatures. Uncertainties in the measurements and energy-balance calculations are discussed. The general meteorological conditions were not extraordinary during the period of the experiment, with a mean 2-m air temperature of −27.5°C, specific humidity of 0.52×10⁻³kg kg⁻¹ and wind speed of 4.1ms⁻¹. The experiment covered the transition period from Antarctic summer (positive net radiation) to winter (negative net radiation), and as a result the period mean net radiation, sensible heat, latent heat and sub-surface heat fluxes were small with values of −1.1, 0.0, −1.0 and 0.7 Wm⁻², respectively. Daily mean net radiation peaked on cloudy days (16 Wm⁻²) and was negative on clear-sky days (minimum of −19 W m⁻²). Daily mean sensible heat flux ranged from −8 to +10 Wm⁻², latent heat flux from −4 to 0 Wm⁻² and sub-surface heat flux from −8 to +7 Wm⁻².     

The 2001 Mesoscale Convective Systems over Iberia and the Balearic Islands

Summary This paper characterizes Mesoscale Convective Systems (MCSs) during 2001 over Iberia and the Balearic Islands and their meteorological settings. Enhanced infrared Meteosat imagery has been used to detect their occurrence over the Western Mediterranean region between June and December 2001 according to satellite-defined criteria based on the MCS physical characteristics. Twelve MCSs have been identified. The results show that the occurrence of 2001 MCSs is limited to the August–October period, with September being the most active period. They tend to develop during the late afternoon or early night, with preferred eastern Iberian coast locations and eastward migrations. A cloud shield area of 50.000 km² is rarely exceeded. When our results are compared with previous studies, it is possible to assert that though 2001 MCS activity was moderate, the convective season was substantially less prolonged than usual, with shorter MCS life cycles and higher average speeds. The average MCS precipitation rate was 3.3 mm·h⁻¹ but a wide range of values varying from scarce precipitation to intense events of 130 mm·24 h⁻¹ (6 September) were collected. The results suggest that, during 2001, MCS rainfall was the principal source of precipitation in the Mediterranean region during the convective season, but its impact varied according to the location. Synoptic analysis based on NCEP/NCAR reanalysis show that several common precursors could be identified over the Western Mediterranean Sea when the 2001 MCSs occurred: a low-level tongue of moist air and precipitable water (PW) exceeding 25 mm through the southern portion of the Western Mediterranean area, low-level zonal warm advection over 2 °C·24 h⁻¹ towards eastern Iberia, a modest 1000–850 hPa equivalent potential temperature (θ_e) difference over 20 °C located close to the eastern Iberian coast, a mid level trough (sometimes a cut-off low) over Northern Africa or Southern Spain and high levels geostrophic vorticity advection exceeding 12·10⁻¹⁰ s⁻² over eastern Iberia and Northern Africa. Finally, the results suggest that synoptic, orographic and a warm-air advection were the most relevant forcing mechanisms during 2001.     

Clear-sky aerosol radiative forcing effects based on multi-site AERONET observations over Europe

Summary One of the great unknowns in climate research is the contribution of aerosols to climate forcing and climate perturbation. In this study, retrievals from AERONET are used to estimate the direct clear-sky aerosol top-of-atmosphere and surface radiative forcing effects for 12 multi-site observing stations in Europe. The radiative transfer code sdisort in the libRadtran environment is applied to accomplish these estimations. Most of the calculations in this study rely on observations which have been made for the years 1999, 2000, and 2001. Some stations do have observations dating back to the year of 1995. The calculations rely on a pre-compiled aerosol optical properties database for Europe. Aerosol radiative forcing effects are calculated with monthly mean aerosol optical properties retrievals and calculations are presented for three different surface albedo scenarios. Two of the surface albedo scenarios are generic by nature bare soil and green vegetation and the third relies on the ISCCP (International Satellite Cloud Climatology Project) data product. The ISCCP database has also been used to obtain clear-sky weighting fractions over AERONET stations. The AERONET stations cover the area 0° to 30° E and 42° to 52° N. AERONET retrievals are column integrated and this study does not make any seperation between the contribution of natural and anthropogenic components. For the 12 AERONET stations, median clear-sky top-of-atmosphere aerosol radiative forcing effect values for different surface albedo scenarios are calculated to be in the range of −4 to −2 W/m². High median radiative forcing effect values of about −6 W/m² were found to occur mainly in the summer months while lower values of about −1 W/m² occur in the winter months. The aerosol surface forcing also increases in summer months and can reach values of −8 W/m². Individual stations often have much higher values by a factor of 2. The median top-of-atmosphere aerosol radiative forcing effect efficiency is estimated to be about −25 W/m² and their respective surface efficiency is around −35 W/m². The fractional absorption coefficient is estimated to be 1.7, but deviates significantly from station to station. In addition, it is found that the well known peak of the aerosol radiative forcing effect at a solar zenith angle of about 75° is in fact the average of the peaks occurring at shorter and longer wavelengths. According to estimations for Central Europe, based on mean aerosol optical properties retrievals from 12 stations, the critical threshold of the aerosol single scattering albedo, between cooling and heating in the presence of an aerosol layer, is close between 0.6 and 0.76.     

Net CO2 exchange of a subarctic mountain birch ecosystem

Summary  Net ecosystem CO₂ exchange was measured over a mountain birch forest in northern Finland throughout the growing season. The maximal net CO₂ uptake rate of about − 0.5 mg(CO₂) m⁻² s⁻¹ was observed at the end of July. The highest nocturnal respiration rates in early August were 0.2 mg(CO₂) m⁻² s⁻¹. The daily CO₂ balances during the time of maximal photosynthesis were about −15 g(CO₂) m⁻² d⁻¹. The mountain birch forest acted as a net sink of CO₂ from 30 June to 28 August. During that period the net CO₂ balance was −448 g(CO₂)m⁻². The interannual representativeness of the observed balances was studied using a simplified daily balance model, with daily mean global radiation and air temperature as the input parameters. The year-to-year variation in the phenological development was parameterised as a function of the cumulative effective temperature sum. The daily balance model was used for estimating the variability in the seasonal CO₂ balances due to the timing of spring and meteorological factors. The sink term of CO₂ in 1996 was lower than the 15-year mean, mainly due to the relatively late emergence of the leaves. Received October 11, 1999 Revised April 25, 2000     

A transient climate change simulation with greenhouse gas and aerosol forcing: projected climate to the twenty-first century

 The potential climatic consequences of increasing atmospheric greenhouse gas (GHG) concentration and sulfate aerosol loading are investigated for the years 1900 to 2100 based on five simulations with the CCCma coupled climate model. The five simulations comprise a control experiment without change in GHG or aerosol amount, three independent simulations with increasing GHG and aerosol forcing, and a simulation with increasing GHG forcing only. Climate warming accelerates from the present with global mean temperatures simulated to increase by 1.7 °C to the year 2050 and by a further 2.7 °C by the year 2100. The warming is non-uniform as to hemisphere, season, and underlying surface. Changes in interannual variability of temperature show considerable structure and seasonal dependence. The effect of the comparatively localized negative radiative forcing associated with the aerosol is to retard and reduce the warming by about 0.9 °C at 2050 and 1.2 °C at 2100. Its primary effect on temperature is to counteract the global pattern of GHG-induced warming and only secondarily to affect local temperatures suggesting that the first order transient climate response of the system is determined by feedback processes and only secondarily by the local pattern of radiative forcing. The warming is accompanied by a more active hydrological cycle with increases in precipitation and evaporation rates that are delayed by comparison with temperature increases. There is an “El Nino-like” shift in precipitation and an overall increase in the interannual variability of precipitation. The effect of the aerosol forcing is again primarily to delay and counteract the GHG-induced increase. Decreases in soil moisture are common but regionally dependent and interannual variability changes show considerable structure. Snow cover and sea-ice retreat. A PNA-like anomaly in mean sea-level pressure with an enhanced Aleutian low in northern winter is associated with the tropical shift in precipitation regime. The interannual variability of mean sea-level pressure generally decreases with largest decreases in the tropical Indian ocean region. Changes to the ocean thermal structure are associated with a spin-down of the Atlantic thermohaline circulation together with a decrease in its variability. The effect of aerosol forcing, although modest, differs from that for most other quantities in that it does not act primarily to counteract the GHG forcing effect. The barotropic stream function in the ocean exhibits modest change in the north Pacific but accelerating changes in much of the Southern Ocean and particularly in the north Atlantic where the gyre spins down in conjunction with the decrease in the thermohaline circulation. The results differ in non-trivial ways from earlier equilibrium 2 × CO₂ results with the CCCma model as a consequence of the coupling to a fully three-dimensional ocean model and the evolving nature of the forcing. Received: 24 September 1998 / Accepted: 8 October 1999     

AGAGE Observations of Methyl Bromide and Methyl Chloride at Mace Head, Ireland, and Cape Grim, Tasmania, 1998–2001

In situ AGAGE GC-MS measurements of methyl bromide (CH₃Br) and methyl chloride (CH₃Cl) at Mace Head, Ireland and Cape Grim, Tasmania (1998–2001) reveal a complex pattern of sources. At Mace Head both gases have well-defined seasonal cycles with similar average annual decreases of 3.0% yr⁻¹ (CH₃Br) and 2.6% yr⁻¹ (CH₃Cl), and mean northern hemisphere baseline mole fractions of 10.37 ± 0.05 ppt and 535.7 ± 2.2 ppt, respectively. We have used a Lagrangian dispersion model and local meteorological data to segregate the Mace Head observations into different source regions, and interpret the results in terms of the known sources and sinks of these two key halocarbons. At Cape Grim CH₃Br and CH₃Cl also show annual decreases in their baseline mixing ratios of 2.5% yr⁻¹ and 1.5% yr⁻¹, respectively. Mean baseline mole fractions were 7.94 ± 0.03 ppt (CH₃Br) and 541.3 ± 1.1 ppt (CH₃Cl). Although CH₃Cl has astrong seasonal cycle there is no well-defined seasonal cycle in the Cape Grim CH₃Br record. The fact that both gases are steadily decreasing in the atmosphere at both locations implies that a change has occurred which is affecting a common, major source of both gases (possibly biomass burning) and/or their major sink process (destruction by hydroxyl radical).     

Kinetic Study of the Reactions of Ozone with Polycyclic Aromatic Hydrocarbons Adsorbed on Atmospheric Model Particles

In this experimental study, rate constants were measured for the reactions of ozone with 13 polycyclic aromatic hydrocarbons (PAHs) adsorbed on different types of particles. Graphite and silica were chosen to model, respectively, carbonaceous and mineral atmospheric particles. The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate PAH concentrations versus time. Second order rate constants were calculated considering the ozone gaseous concentration. At room temperature, rate constants varied, in the case of graphite particles, between (1.5 ± 0.5) × 10⁻¹⁷ and (1.3 ± 0.7) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for chrysene and dibenzo[a,l]pyrene, respectively, and, in the case of silica particles, between (1.5 ± 0.3) × 10⁻¹⁷ and (1.4 ± 0.3) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for fluoranthene and benzo[a]pyrene, respectively. Different granulometric parameters (particle size, pore size) and different PAH concentrations were tested in the case of silica particles. Heterogeneous reactions of ozone with particulate PAHs are shown to be more rapid than those occurring in the gas-phase, and may be competitive with atmospheric photodegradation.     

Water interaction with MgCl<Subscript>2</Subscript>×6H<Subscript>2</Subscript>O and NaCl surfaces: measurements of the uptake coefficient

The uptake of water vapor on MgCl₂×6H₂O and NaCl salt dry solid films was studied over the temperature range 240 to 340 K and at 1 Torr pressure of helium using a flow reactor coupled to a modulated molecular beam mass spectrometer. The H₂O to salt uptake data were obtained from the kinetics of H₂O loss on salt coated Pyrex rods. The following Arrhenius expression was obtained for the initial uptake coefficient of H₂O on MgCl₂×6H₂O films: γ ₀ (MgCl₂) = (6.5 ± 1.0) × 10⁻⁶ exp[(470 ± 40)/T] (calculated with specific BET surface area, quoted uncertainties are 1σ statistical). The rate of H₂O adsorption on NaCl was found to be much lower than on MgCl₂×6H₂O, and only an upper limit was determined for the corresponding uptake coefficient: γ (NaCl) ≤ 5.6 × 10⁻⁶ at T = 300 K. The results show that the rate of H₂O adsorption to salt surfaces is drastically dependent on the salt sample composition.     

Methodology of analysis associating survey results by the filter-pack method with those of precipitation- Acid-base balance on acid-related and alkali-related chemical species in urban ambient air and its influence on the acidification of precipitation -

Continuous weekly monitoring on the concentration of gases and aerosols in urban ambient air by a four-stage filter-pack method was carried out for 7 years in order to study not only the acid-base balance of acid-related (HNO₃, NO₃ ⁻, and non-sea-salt-(nss-)SO₄ ²⁻) and alkali-related (NH₃, NH₄ ⁺, and nss-Ca²⁺) chemical species but also its influence on the acidification of precipitation. The concentrations of the total nitrate (= NO₃⁻ + HNO₃) and nss-SO₄²⁻ showed a similar seasonal variation: high in the summer and low in the winter. The total nitrate and nss-SO₄²⁻ accounted for 0.43 and 0.57 of the acid-related species, respectively, on an equivalent basis. The total ammonium (= NH₃ + NH₄⁺) accounted for more than 0.9 of the alkali-related species, except for a springtime nss-Ca²⁺ episodic peak. The alkali-related species were generally overabundant compared with the acid-related species in the HNO₃-NO₃⁻-nss-SO₄²⁻-NH₃-NH₄⁺-nss-Ca²⁺ system. The alkali-rich distribution was especially pronounced in the winter, but the acid-related species was comparable to the alkali-related species in the summer, which was attributed to the larger H⁺ deposition by precipitation in the summer. This study can provide a methodology to associate survey results obtained by a filter-pack method with those of precipitation.     

The temporal trend of stratospheric carbonyl sulfide

Using a database of spectra collected with an airborne infrared spectrometer between 1978 and 2005, the longest record of this type, we have searched for a temporal trend in the stratospheric OCS amount. The total column above 200 hPa, in latitudes from 30° to 60°N, shows a change of about 0.77 ± 0.80% per year relative to the 2010 value which is 1.34 × 10¹⁵ molecules cm⁻²; thus not a significant change. Observations are made from the base of the stratosphere and are uniquely suited to determining the stratospheric OCS abundance.