Seasonal variation of bromocarbons at Hateruma Island,Japan: implications for global sources

High-frequency measurements of dibromomethane (CH₂Br₂) and bromoform (CHBr₃) at Hateruma Island, in the subtropical East China Sea, were performed using automated preconcentration gas chromatography/mass spectrometry. Their baseline concentrations, found in air masses from the Pacific Ocean, were 0.65 and 0.26 ppt, respectively, in summer and 1.08 and 0.87 ppt, respectively, in winter. Air masses transported from Southeast Asia were rich in bromocarbons, suggesting strong emissions in this area. The passage of cold fronts from the Asian continent was associated with sharp increases in observed concentrations of bromocarbons derived from coastal regions of the continent. Comparison of the relationships between [CH₂Br₂]/[CHBr₃] and [CHBr₃] in the Hateruma Island data with those in monthly mean data from 14 globally distributed U.S. National Oceanic and Atmospheric Administration ground stations suggested that these gases are produced primarily from a common process on a global scale.     

Regional Sources of Methyl Chloride, Chloroform and Dichloromethane Identified from AGAGE Observations at Cape Grim, Tasmania, 1998–2000

There are large uncertainties in identifying and quantifying the natural and anthropogenic sources of chloromethanes – methyl chloride (CH₃Cl), chloroform (CHCl₃) and dichloromethane (CH₂Cl₂), which are responsible for about 15% of the total chlorine in the stratosphere. We report two years of in situ observations of these species from the AGAGE (Advanced Global Atmospheric Gas Experiment) program at Cape Grim, Tasmania (41° S, 145° E). The average background levels of CH₃Cl, CHCl₃ and CH₂Cl₂ during 1998–2000 were 551± 8, 6.3± 0.2 and 8.9± 0.2 ppt (dry air mole fractions expressed in parts per 10¹²) respectively, with a two-year average amplitude of the seasonal cycles in background air of 25, 1.1 and 1.5 ppt respectively. The CH₃Cl and CHCl₃ records at Cape Grim show clear episodes of elevated mixing ratios up to 1300 ppt and 55 ppt respectively, which are highly correlated, suggesting common source(s). Trajectory analyses show that the sources of CH₃Cl and CHCl₃ that are responsible for these elevated observations are located in coastal-terrestrial and/or coastal-seawater regions in Tasmania and the south-eastern Australian mainland. Elevated levels of CH₂Cl₂ (up to 70 ppt above background) are associated mainly with emissions from the Melbourne/Port Phillip region, a large urban/industrial complex (population 3.5 million) 300 km north of Cape Grim.Now at the Centre for Atmospheric ChemistryNow at School of Environmental Sciences     

Simulated Spatial Distribution and Seasonal Variation of Atmospheric Methane over China: Contributions from Key Sources简

We used the global atmospheric chemical transport model,GEOS-Chem,to simulate the spatial distribution and seasonal variation of surface-layer methane （CH4） in 2004,and quantify the impacts of individual domestic sources and foreign transport on CH4 concentrations over China.Simulated surface-layer CH4 concentrations over China exhibit maximum concentrations in summer and minimum concentrations in spring.The annual mean CH4 concentrations range from 1800 ppb over western China to 2300 ppb over the more populated eastern China.Foreign emissions were found to have large impacts on CH4 concentrations over China,contributing to about 85％ of the CH4 concentrations over western China and about 80％ of those over eastern China.The tagged simulation results showed that coal mining,livestock,and waste are the dominant domestic contributors to CH4 concentrations over China,accounting for 36％,18％,and 16％,respectively,of the annual and national mean increase in CH4 concentration from all domestic emissions.Emissions from rice cultivation were found to make the largest contributions to CH4 concentrations over China in the summer,which is the key factor that leads to the maximum seasonal mean CH4 concentrations in summer.     

Identification of Regional Sources of Methyl Bromide and Methyl Iodide from AGAGE Observations at Cape Grim,Tasmania

There are large uncertainties in identifying and quantifying the globally significant sources and sinks of methyl bromide (CH₃Br) and methyl iodide (CH₃I). Long-term, quasi-continuous observations can provide valuable information about their regional sources, which may be significant in the global context. We report 3 years of in situobservations of these trace gases from the AGAGE (Advanced Global Atmospheric Gas Experiment) program at Cape Grim, Tasmania (41 °S, 145 °E). The average background levels of CH₃Br and CH₃I during March 1998–March 2001 were 8.05 and 1.39 ppt (dry air mole fractions expressed in parts per 10¹²), respectively. The CH₃Br background data showed little seasonal variability. Trajectory analyses reveal that air masses showing elevated CH₃Br levels at Cape Grim have had significant contact with coastal-terrestrial and/or coastal-seawater and/or urban source regions. The CH₃I background data showed a seasonal cycle with a 3-year average amplitude of 0.47 ppt and maximum concentrations in summer, suggesting that the Southern Ocean is a significant source.Trajectory analyses reveal that air masses showing highly elevated CH₃I levels at Cape Grim have had significant contact with coastal-terrestrial and/or coastal-seawater regions and/or the open-ocean regions of Bass Strait and the Tasman Sea.     

Seasonal variation of volatile organic iodine compounds in the water column of Funka Bay,Hokkaido, Japan

Volatile organic iodine compounds (VOIs) emitted from the ocean surface to the air play an important role in atmospheric chemistry. Shipboard observations were conducted in Funka Bay, Hokkaido, Japan, bimonthly or monthly from March 2012 to December 2014, to elucidate the seasonal variations of VOI concentrations in seawater and their sea-to-air iodine fluxes. The bay water exchanges with the open ocean water of the North Pacific twice a year (early spring and autumn). Vertical profiles of CH₂I₂, CH₂ClI, CH₃I, and C₂H₅I concentrations in the bay water were measured bimonthly or monthly within an identified water mass. The VOI concentrations began to increase after early April at the end of the diatom spring bloom, and represented substantial peaks in June or July. The temporal variation of the C₂H₅I profile, which showed a distinct peak in the bottom layer from April to July, was similar to the PO₄ ^3? variation profile. Correlation between C₂H₅I and PO₄ ^3? concentrations (r = 0.93) suggests that C₂H₅I production was associated with degradation of organic matter deposited on the bottom after the spring bloom. CH₂I₂ and CH₂ClI concentrations increased substantially in the surface and subsurface layers (0–60 m) in June or July resulted in a clear seasonal variation of the sea-to-air iodine flux of the VOIs (high in summer or autumn and low in spring).     

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).     

Analysis of the origins and implications of the18O content of stratospheric water vapor

Factors influencing the¹⁸O content of stratospheric H₂O are reviewed in order to provide a theoretical framework for the interpretation of measurements of this quantity, which are now becoming available. Depletions in¹⁸O of 5–10% in stratospheric H₂O are expected based on the known correlation between that of D and¹⁸O in tropospheric H₂O and observed measurements of large (typically 50%) depletions of D in stratospheric H₂O. H₂O formed in the stratosphere as a result of oxidation of CH₄ can be expected to reflect primarily the¹⁸O content of stratospheric O₂, which is the same as that of tropospheric O₂ (slightly enhanced with respect to standard mean ocean water). Thus, a reduction in the¹⁸O depletion is expected with increasing altitude, but not a large enhancement in¹⁸O in upper stratospheric H₂O as found in recent far infrared measurements. The observed large enhancement of¹⁸O in stratospheric O₃ is not expected to be reflected in stratospheric H₂O. Necessary laboratory data for the improved quantification of these effects are reviewed.     

Emission estimates of methyl chloride from industrial sources in China based on high frequency atmospheric observations

Methyl Chloride (CH₃Cl) is a chlorine-containing trace gas in the atmosphere contributing significantly to stratospheric ozone depletion (Carpenter et al. 2014). In the global CH₃Cl budget, the atmospheric CH₃Cl emissions is predominantly maintained by natural sources, of which magnitudes have been relatively well-constrained. However, significant uncertainties still remain in the CH₃Cl emission strengths from anthropogenic sources. High-frequency and high-precision in situ measurements of atmospheric CH₃Cl concentrations obtained since 2008 at Gosan station (a remote background site in the East Asia) reveal significant pollution events superimposed on the seasonally varying regional background levels. Back trajectory statistics showed that air masses corresponding to the observed CH₃Cl enhancement largely originated from regions of intensive industrial activities in China. Based on an inter-species correlation method, estimates of CH₃Cl emissions from manufacturing industries including coal combustion, use of feedstocks, or process agents in chemical production for China (2008–2012) are 297 ± 71 Gg yr.^?1 in 2008 to 480 ± 99 Gg yr.^?1 in 2009, followed by a gradual decrease of about 25% between 2009 and 2012 (398 ± 92 Gg yr.^?1 for 2010; 286 ± 68 Gg yr.^?1 for 2011; 358 ± 92 Gg yr.^?1 for 2012). The annual average of industrial CH₃Cl emissions for 2008–2012 (363 ± 85 Gg yr.^?1) in China is comparable to the known total global anthropogenic CH₃Cl emissions accounting only for coal combustion and indoor biofuel use. This may suggest that unless emissions from the chemical industry are accounted for, global anthropogenic emissions of CH₃Cl have been substantially underestimated. In particular, since industrial production and use of CH₃Cl have not been regulated under the Montreal Protocol (MP) or its successor amendments, continuous monitoring of Chinese CH₃Cl outflow is important to properly evaluate its anthropogenic emissions.     

Impacts of Global Emissions of CO, NOx, and CH4 on China Tropospheric Hydroxyl Free Radicals

Using the global chemistry and transport model MOZART,the simulated distributions of tropospheric hydroxyl free radicals(OH) over China and its sensitivities to global emissions of carbon monoxide(CO),nitrogen oxide(NO x),and methane(CH 4) were investigated in this study.Due to various distributions of OH sources and sinks,the concentrations of tropospheric OH in east China are much greater than in west China.The contribution of NO + perhydroxyl radical(HO 2) reaction to OH production in east China is more pronounced than that in west China,and because of the higher reaction activity of non-methane volatile organic compounds(NMVOCs),the contributions to OH loss by NMVOCs exceed those of CO and take the dominant position in summer.The results of the sensitivity runs show a significant increase of tropospheric OH in east China from 1990 to 2000,and the trend continues.The positive effect of double emissions of NO x on OH is partly offset by the contrary effect of increased CO and CH 4 emissions:the double emissions of NO x will cause an increase of OH of 18.1%-30.1%,while the increases of CO and CH 4 will cause a decrease of OH of 12.2%-20.8% and 0.3%-3.0%,respectively.In turn,the lifetimes of CH 4,CO,and NO x will increase by 0.3%-3.1% with regard to double emissions of CH 4,13.9%-26.3% to double emissions of CO and decrease by 15.3%-23.2% to double emissions of NO x.     

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).     

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.     

Ocean acidification and climate change: synergies and challenges of addressing both under the UNFCCC

Ocean acidification and climate change are linked by their common driver: CO₂. Climate change is the consequence of a range of GHG emissions, but ocean acidification on a global scale is caused solely by increased concentrations of atmospheric CO₂. Reducing CO₂ emissions is therefore the most effective way to mitigate ocean acidification. Acting to prevent further ocean acidification by reducing CO₂ emissions will also provide simultaneous benefits by alleviating future climate change. Although it is possible that reducing CO₂ emissions to a level low enough to address ocean acidification will simultaneously address climate change, the reverse is unfortunately not necessarily true. Despite the ocean's integral role in the climate system and the potentially wide-ranging impacts on marine life and humans, the problem of ocean acidification is largely absent from most policy discussions pertaining to CO₂ emissions. The linkages between ocean acidification, climate change and the United Nations Framework Convention on Climate Change (UNFCCC) are identified and possible scenarios for developing common solutions to reduce and adapt to ocean acidification and climate change are offered. Areas where the UNFCCC is currently lacking capacity to effectively tackle rising ocean acidity are also highlighted.     

未来甲烷排放增加对平流层水汽和全球臭氧的影响

利用一个耦合的大气化学-气候模式(WACCM3)研究了地表甲烷排放增加对平流层水汽和全球臭氧变化的影响.结果表明,如果地表甲烷的排放量在2000年的基础上增加50%(达到政府间气候变化专门委员会A1B排放情景中2050年的值),平流层水汽体积分数将平均增加约0.8×10^-6.南半球平流层甲烷转化为水汽的效率比北半球高.在北半球平流层中,1mol甲烷分子可以转化为约1.63mol的水汽分子,而在南半球1mol甲烷分子大概可以转化为约1.82mol的水汽分子.甲烷排放增加50%将使全球中低纬度地区以及北半球高纬度地区的臭氧柱总量增加1%-3%,使南半球高纬度地区臭氧柱总量增加近8%,而秋季(南半球春季)南极地区臭氧柱总量增加幅度可高达20%,南极臭氧的这种显着增加主要是由于甲烷增加造成的化学反馈所致.在北半球中高纬度地区,甲烷增加引起的臭氧变化主要与甲烷氧化导致的水汽增加有关.研究还表明,未来甲烷排放增加对臭氧的恢复作用其实与溴化物排放的减少一样重要.     

European sources of halocarbons and nitrous oxide: Update 1986

Semi-continuous measurements of CFCl₃, CF₂Cl₂, CCl₄, CH₃CCl₃ and N₂O were made at Adrigole, Ireland as part of the Atmospheric Lifetime Experiment (ALE). Clean, baseline air from the Atlantic Ocean was measured approximately 70% of the time; pollution events from Europe, for the remainder. The two final years of ALE data from Adrogole give a five-year record from July 1978 to June 1983. This paper extends previous work on the relative enhancements of trace gases during pollution episodes and presents (1) unambiguous identification of elevated levels of N₂O concurrent with halocarbon pollution events, (2) detection of trends in emission of CH₃CCl₃, (3) discovery of seasonal variations in emission of CF₂Cl₂, CCl₄ and CH₃CCl₃, (4) characterization of typical summer and winter pollution episodes, and (5) identification of weather patterns over Europe that are associated with high concentrations of CFCs at Adrigole. Some of these results assume that CFCl₃ represents a uniform, well buffered source from the continent. The latter two results are particularly useful in the testing and calibration of three-dimensional chemical transport models. Observed enhancements are marginally consistent with estimates of halocarbon use by the chemical industry. The source of nitrous oxide correlated with halocarbons is 0.8 Tg(N)/yr from Europe alone and represents approximately 10% of the global stratospheric loss.     

Chemistry of organic traces in air

The occurrence of CH₂Br₂, CH₂BrCl, CH₂I₂, CH₂ClI, CHBr₃, CHBr₂Cl, CHBrCl₂ and CH₂Br-CH₂Br in marine air and seawater from various sampling sites in the region of the Atlantic Ocean have been measured and evaluated. A correlation exists between high concentrations of these compounds in air and in water and the occurrence of algae at the coastlines of various islands (The Azores, Bermuda, Tenerife) and in a region of high bioactivity in the Atlantic Ocean near the West African coast.Real-world air-water concentration ratios derived from measurements in the open ocean identify the water mass near the African coast with its high primary production as a source for the above compounds. This region has to be discussed also as a possible secondary source in which CHBr₂Cl, CHBrCl₂ and CH₂ClI can be formed via halogen-exchange. Whether CHBrCl₂ and CH₂ClI under-go transformation to CHCl₃ and CH₂Cl₂, respectively, is open to further investigations.Direct photolysis and degradation by OH-radicals lead to a gradient in the marine troposphere with reduced concentrations for the organobromides above the tropospheric boundary layer.Partly presented at: 2nd International Symposium on Biosphere-Atmosphere Exchange, Mainz, F.R.Germany, 16–21 March, 1986. Part VII: Chemosphere 15 (1986) 429–436.     

Climatic changes associated with a global “2°C-stabilization” scenario simulated by the ECHAM5/MPI-OM coupled climate model

In this study, concentrations of the well-mixed greenhouse gases as well as the anthropogenic sulphate aerosol load and stratospheric ozone concentrations are prescribed to the ECHAM5/MPI-OM coupled climate model so that the simulated global warming does not exceed 2°C relative to pre-industrial times. The climatic changes associated with this so-called “2°C-stabilization” scenario are assessed in further detail, considering a variety of meteorological and oceanic variables. The climatic changes associated with such a relatively weak climate forcing supplement the recently published fourth assessment report by the IPCC in that such a stabilization scenario can only be achieved by mitigation initiatives. Also, the impact of the anthropogenic sulphate aerosol load and stratospheric ozone concentrations on the simulated climatic changes is investigated. For this particular climate model, the 2°C-stabilization scenario is characterized by the following atmospheric concentrations of the well-mixed greenhouse gases: 418 ppm (CO₂), 2,026 ppb (CH₄), and 331 ppb (N₂O), 786 ppt (CFC-11) and 486 ppt (CFC-12), respectively. These greenhouse gas concentrations correspond to those for 2020 according to the SRES A1B scenario. At the same time, the anthropogenic sulphate aerosol load and stratospheric ozone concentrations are changed to the level in 2100 (again, according to the SRES A1B scenario), with a global anthropogenic sulphur dioxide emission of 28 TgS/year leading to a global anthropogenic sulphate aerosol load of 0.23 TgS. The future changes in climate associated with the 2°C-stabilization scenario show many of the typical features of other climate change scenarios, including those associated with stronger climatic forcings. That are a pronounced warming, particularly at high latitudes accompanied by a marked reduction of the sea-ice cover, a substantial increase in precipitation in the tropics as well as at mid- and high latitudes in both hemispheres but a marked reduction in the subtropics, a significant strengthening of the meridional temperature gradient between the tropical upper troposphere and the lower stratosphere in the extratropics accompanied by a pronounced intensification of the westerly winds in the lower stratosphere, and a strengthening of the westerly winds in the Southern Hemisphere extratropics throughout the troposphere. The magnitudes of these changes, however, are somewhat weaker than for the scenarios associated with stronger global warming due to stronger climatic forcings, such as the SRES A1B scenario. Some of the climatic changes associated with the 2°C-stabilization are relatively strong with respect to the magnitude of the simulated global warming, i.e., the pronounced warming and sea-ice reduction in the Arctic region, the strengthening of the meridional temperature gradient at the northern high latitudes and the general increase in precipitation. Other climatic changes, i.e., the El Niño like warming pattern in the tropical Pacific Ocean and the corresponding changes in the distribution of precipitation in the tropics and in the Southern Oscillation, are not as markedly pronounced as for the scenarios with a stronger global warming. A higher anthropogenic sulphate aerosol load (for 2030 as compared to the level in 2100 according to the SRES A1B scenario) generally weakens the future changes in climate, particularly for precipitation. The most pronounced effects occur in the Northern Hemisphere and in the tropics, where also the main sources of anthropogenic sulphate aerosols are located.     

The distribution of light nonmethane hydrocarbons over the mid-Atlantic: Results of the Polarstern cruise ANT VII/1

During the cruise ANT VII/1 (September/October 1988) of the German research vessel Polarstern the latitudinal distributions of several nonmethane hydrocarbons were measured over the Atlantic between 45°N and 30°S by in-situ gas chromatography.On the average, the highest mixing ratios of ethane, propane, i- and n-butane, ethene and acetylene were observed in the Northern Hemisphere around 40° N and just north of the intertropical convergence zone, respectively. South of the equator, a bulge in the mixing ratios of ethane and acetylene was observed indicating aged biomass burning emissions. This observation coincided with enhanced tropospheric ozone found in this region at this season. On the average ethane and acetylene mixing ratios were around 500 and 100 ppt, respectively, whereas the levels of the other NMHC were in the range of some ppt up to 100 ppt.compared with the results of the cruise ANT V/5 (March/April, 1987), the ethane mixing ratios in September/October proved to be a factor of 3 lower in the Northern Hemisphere and a factor of 2 higher in the Southern Hemisphere, probably due to seasonal effects. Possible causes are the higher OH radical concentrations in summer, which result in a faster removal of ethane or stronger emission from biomass burning which also peaks in the dry season.The relative pattern of the hydrocarbons just north of the ITCZ was very similar for both measurement series. In this region, the NMHC were advected by long-range transport from the continent, whereas generally the ocean itself acts as a major NMHC source. This is supported by the results of a balance calculation between oceanic emissions and atmospheric removal rates.     

Scenarios of possible changes in atmospheric temperatures and ozone concentrations due to man's activities,estimated with a one-dimensional coupled photochemical climate model

A one-dimensional coupled climate and chemistry model has been developed to estimate past and possible future changes in atmospheric temperatures and chemical composition due to human activities. The model takes into account heat flux into the oceans and uses a new tropospheric temperature lapse rate formulation. As found in other studies, we estimate that the combined greenhouse effect of CH₄, O₃, CF₂Cl₂, CFCl₃ and N₂O in the future will be about as large as that of CO₂. Our model calculates an increase in average global surface temperatures by about 0.6°C since the start of the industrial era and predicts for A.D. 2050 a twice as large additional rise. Substantial depletions of ozone in the upper stratosphere by between 25% and 55% are calculated, depending on scenario. Accompanying temperature changes are between 15°C and 25°C. Bromine compounds are found to be important, if no rigid international regulations on CFC emissions are effective. Our model may, however, concivably underestimate possible effects of CFCl₃, CF₂Cl₂, C₂F₃Cl₃ and other CFC and organic bromine emissions on lower stratospheric ozone, because it can not simulate the rapid breakdown of ozone which is now being observed worldwide. An uncertainty study regarding the photochemistry of stratospheric ozone, especially in the region below about 25 km, is included. We propose a reaction, involving excited molecular oxygen formation from ozone photolysis, as a possible solution to the problem of ozone concentrations calculated to be too low above 45 km. We also estimate that tropospheric ozone concentrations have grown strongly in the northern hemisphere since pre-industrial times and that further large increases may take place, especially if global emissions of NO_x from fossil fuel and biomass burning were to continue to increase. Growing NO_x emissions from aircraft may play an important role in ozone concentrations in the upper troposphere and low stratosphere.     

Airborne measurements of dimethylsulfide,sulfur dioxide,and aerosol ions over the Southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO₂), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO₄ ^2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10^–12; 24 ppt=1 nmol m^–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m^–2 d^–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO₂ concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO₂ in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO₂. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO₂ by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO₂ and one-third to MSA. On the other hand, MSA/nss-SO₄ ^2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO₄ ^2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO₂, nss-SO₄ ^2- values decreased significantly in the middle FT. NH₄ ⁺/nss-SO₄ ^2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.     

The Synergism between Methanogens and Methanotrophs and the Nature of their Contributions to the Seasonal Variation of Methane Fluxes in a Wetland: The Case of Dajiuhu Subalpine Peatland

Wetland ecosystems are the most important natural methane (CH₄) sources, whose fluxes periodically fluctuate. Methanogens (methane producers) and methanotrophs (methane consumers) are considered key factors affecting CH₄ fluxes in wetlands. However, the symbiotic relationship between methanogens and methanotrophs remains unclear. To help close this research gap, we collected and analyzed samples from four soil depths in the Dajiuhu subalpine peatland in January, April, July, and October 2019 and acquired seasonal methane flux data from an eddy covariance (EC) system, and investigated relationships. A phylogenetic molecular ecological networks (pMENs) analysis was used to identify keystone species and the seasonal variations of the co-occurrence patterns of methanogenic and methanotrophic communities. The results indicate that the seasonal variations of the interactions between methanogenic and methanotrophic communities contributed to CH₄ emissions in wetlands. The keystone species discerned by the network analysis also showed their importance in mediating CH₄ fluxes. Methane (CH₄) emissions in wetlands were lowest in spring; during this period, the most complex interactions between microbes were observed, with intense competition among methanogens while methanotrophs demonstrated better cooperation. Reverse patterns manifested themselves in summer when the highest CH₄ flux was observed. Methanoregula formicica was negatively correlated with CH₄ fluxes and occupied the largest ecological niches in the spring network. In contrast, both Methanocella arvoryzae and Methylocystaceae demonstrated positive correlations with CH₄ fluxes and were better adapted to the microbial community in the summer. In addition, soil temperature and nitrogen were regarded as significant environmental factors to CH₄ fluxes. This study was successful in explaining the seasonal patterns and microbial driving mechanisms of CH₄ emissions in wetlands.