Comparison of emissions estimates derived from atmospheric measurements with national estimates of HFCs,PFCs and SF6

This paper assesses the feasibility of using atmospheric measurement of fluorinated greenhouse gases (HFCs, PFCs and SF6) for the review and verification of greenhouse gas inventories provided by national governments. For this purpose, available data were compiled. It was found that atmospheric measurements of these gases are available and provide an indication of global annual emissions with sufficient certainty to reach the following conclusions: Within the uncertainty of the method, it was found that emissions of HFC-23, a by-product of HCFC-22 production, as obtained from atmospheric measurements did not decrease as fast, as the countries have reported. In contrast, SF6 concentrations in the atmosphere suggest higher emissions than reported by countries. Regional emission estimates from atmospheric measurements are still in a more pioneering state and cannot be compared to national estimates. Intensified efforts to measure HFCs, PFCs and SF6 in the atmosphere are recommended.     

Ambient halocarbon mixing ratios in 45 Chinese cities

During this study 158 whole air samples were collected in 45 Chinese cities in January and February 2001. The spatial distribution of different classes of halocarbons in the Chinese urban atmosphere, including chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), Halon-1211, and other chlorinated compounds is presented and discussed. Most of these compounds were enhanced compared to background levels. However, the mean enhancement of CFCs was relatively small, with CFC-12 and CFC-11 increases of 6% (range 1–31%) and 10% (range 2–89%), respectively, with respect to the global background. On the contrary, strongly enhanced levels of CFC replacement compounds and halogenated compounds used as solvents were measured. The average Halon-1211 concentration exceeded the background of 4.3 pptv by 75% and was higher than 10 pptv in several cities. Methyl chloride mixing ratios were also strongly elevated (78% higher than background levels), which is likely related to the widespread use of coal and biofuel in China.     

An overview of environmental hazards and exposure risk of hydrofluorocarbons (HFCs)

Hydrofluorocarbons (HFCs) are being used as replacements for chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that cause significantly stratospheric ozone depletion and global warming. HFCs under commercial uses as cleaning solvents in the electronic components, blowing agent in the foamed plastics, refrigerant in the air conditioning units and refrigerators, fire suppression agent in the fire protection, propellant in the metered dose inhalers (MDIs), and dry etching agent in the semiconductor manufacturing. Among these HFCs, 1,1,1,2-tetrafluoroethane (HFC-134a) is the most widely used one. From the environmental, ecological, and health points of view, it is urgent to mitigate and control the emissions of these HFCs from a diversity of commercial applications and industrial processes. This article aims to introduce these HFCs in commercial uses and environmental hazards (i.e., global warming, photochemical potential, flammability safety, environmental partition and ecotoxicity). Further, the updated data on the human toxicity, occupational exposure and health risk of these HFCs (esp., HFC-134a) are addressed in this review paper.     

Cloud Albedo,Greenhouse Effects,Atmospheric Chemistry,and Climate Change

Changes in global atmospheric chemistry and climate are taking place as a result of observed trends in long-lived species such as CO₂, CH₄, N₂O, and the CFCs. The continuation of these trends is expected to eventually lead to a major atmospheric warming that might profoundly affect the society we live in. Trends in short-lived species such as NOx and SOx are also suspected. These trends are not as well established, because the shorter-lived species vary spatially and temporally. Trends in NOx would be expected to lead to increases in tropospheric ozone that would add to the warming created by the other greenhouse gases. Trends in NOx could also alter tropospheric OH concentrations that could lead to changes in CH₄ and some of the CFCs. On the other hand, increases in sulfur emissions may alter cloud optical properties. The changes in cloud optical properties could possibly offset the warming expected from increases in greenhouse gases, depending on the role of natural oceanic sulfur emissions. This paper summarizes recent research in these areas and the interactions of climate and atmospheric chemistry.     

Halogenated compounds and climate change: future emission levels and reduction costs

OBJECTIVES: This work assesses the contribution to climate change resulting from emissions of the group of halogenated greenhouse gases. METHODS: A bottom-up emission model covering 22 technological sectors in four major regions is described. Emission estimates for 1996 and projection for 2010 and 2020 are presented. The costs for deep cuts into projected emission levels are calculated. RESULTS: The substances covered by this study have contributed emissions of 1100 +/- 800 MT CO2 equivalents per year in 1996. In terms of their relative contribution to emissions of CO2 equivalents, this corresponds to 3 +/- 2% of global emissions of all anthropogenic greenhouse gases. The wide range of uncertainty is due to the poorly quantified net global warming potential of the ozone depleting substances, which have an indirect cooling effect on climate through the destruction of stratospheric ozone. For annual emissions of HFCs, PFCs and SF6 (which are regulated under the Kyoto Protocol and for which global warming potentials are well defined), the relative contribution is projected to increase to 2% (600 MT CO2 eq.) of global greenhouse gas emissions by 2010. This trend is expected to continue, emissions are projected to grow to a contribution of roughly 3% (870 MT CO2 eq.) in 2020 compared to 0.9% (300 MT CO2 eq.) in 1996. For HFCs, PFCs and SF6, this study identifies global emission reduction potentials of 260 MT CO2 eq. per year in 2010 and 640 MT CO2 eq. per year in 2020 at below US$ 50 per ton. These values correspond to roughly 40% and 75% of projected emissions in 2010 and 2020, respectively.     

Atmospheric composition change: Climate–Chemistry interactions

Chemically active climate compounds are either primary compounds like methane (CH₄), removed by oxidation in the atmosphere, or secondary compounds like ozone (O₃), sulfate and organic aerosols, both formed and removed in the atmosphere. Man-induced climate–chemistry interaction is a two-way process: Emissions of pollutants change the atmospheric composition contributing to climate change through the aforementioned climate components, and climate change, through changes in temperature, dynamics, the hydrological cycle, atmospheric stability, and biosphere-atmosphere interactions, affects the atmospheric composition and oxidation processes in the troposphere. Here we present progress in our understanding of processes of importance for climate–chemistry interactions, and their contributions to changes in atmospheric composition and climate forcing. A key factor is the oxidation potential involving compounds like O₃ and the hydroxyl radical (OH). Reported studies represent both current and future changes. Reported results include new estimates of radiative forcing based on extensive model studies of chemically active climate compounds like O₃, and of particles inducing both direct and indirect effects. Through EU projects like ACCENT, QUANTIFY, and the AeroCom project, extensive studies on regional and sector-wise differences in the impact on atmospheric distribution are performed. Studies have shown that land-based emissions have a different effect on climate than ship and aircraft emissions, and different measures are needed to reduce the climate impact. Several areas where climate change can affect the tropospheric oxidation process and the chemical composition are identified. This can take place through enhanced stratospheric–tropospheric exchange of ozone, more frequent periods with stable conditions favoring pollution build up over industrial areas, enhanced temperature induced biogenic emissions, methane releases from permafrost thawing, and enhanced concentration through reduced biospheric uptake. During the last 5–10 years, new observational data have been made available and used for model validation and the study of atmospheric processes. Although there are significant uncertainties in the modeling of composition changes, access to new observational data has improved modeling capability. Emission scenarios for the coming decades have a large uncertainty range, in particular with respect to regional trends, leading to a significant uncertainty range in estimated regional composition changes and climate impact.     

Global change: state of the science

Only recently, within a few decades, have we realized that humanity significantly influences the global environment. In the early 1980s, atmospheric measurements confirmed basic concepts developed a decade earlier. These basic concepts showed that human activities were affecting the ozone layer. Later measurements and theoretical analyses have clearly connected observed changes in ozone to human-related increases of chlorine and bromine in the stratosphere. As a result of prompt international policy agreements, the combined abundances of ozone-depleting compounds peaked in 1994 and ozone is already beginning a slow path to recovery. A much more difficult problem confronting humanity is the impact of increasing levels of carbon dioxide and other greenhouse gases on global climate. The processes that connect greenhouse gas emissions to climate are very complex. This complexity has limited our ability to make a definitive projection of future climate change. Nevertheless, the range of projected climate change shows that global warming has the potential to severely impact human welfare and our planet as a whole. This paper evaluates the state of the scientific understanding of the global change issues, their potential impacts, and the relationships of scientific understanding to policy considerations.     

Air pollution,greenhouse gases and climate change: Global and regional perspectives

Greenhouse gases (GHGs) warm the surface and the atmosphere with significant implications for rainfall, retreat of glaciers and sea ice, sea level, among other factors. About 30 years ago, it was recognized that the increase in tropospheric ozone from air pollution (NO_x, CO and others) is an important greenhouse forcing term. In addition, the recognition of chlorofluorocarbons (CFCs) on stratospheric ozone and its climate effects linked chemistry and climate strongly. What is less recognized, however, is a comparably major global problem dealing with air pollution. Until about ten years ago, air pollution was thought to be just an urban or a local problem. But new data have revealed that air pollution is transported across continents and ocean basins due to fast long-range transport, resulting in trans-oceanic and trans-continental plumes of atmospheric brown clouds (ABCs) containing sub micron size particles, i.e., aerosols. ABCs intercept sunlight by absorbing as well as reflecting it, both of which lead to a large surface dimming. The dimming effect is enhanced further because aerosols may nucleate more cloud droplets, which makes the clouds reflect more solar radiation. The dimming has a surface cooling effect and decreases evaporation of moisture from the surface, thus slows down the hydrological cycle. On the other hand, absorption of solar radiation by black carbon and some organics increase atmospheric heating and tend to amplify greenhouse warming of the atmosphere.ABCs are concentrated in regional and mega-city hot spots. Long-range transport from these hot spots causes widespread plumes over the adjacent oceans. Such a pattern of regionally concentrated surface dimming and atmospheric solar heating, accompanied by widespread dimming over the oceans, gives rise to large regional effects. Only during the last decade, we have begun to comprehend the surprisingly large regional impacts. In S. Asia and N. Africa, the large north-south gradient in the ABC dimming has altered both the north-south gradients in sea surface temperatures and land–ocean contrast in surface temperatures, which in turn slow down the monsoon circulation and decrease rainfall over the continents. On the other hand, heating by black carbon warms the atmosphere at elevated levels from 2 to 6 km, where most tropical glaciers are located, thus strengthening the effect of GHGs on retreat of snow packs and glaciers in the Hindu Kush-Himalaya-Tibetan glaciers.Globally, the surface cooling effect of ABCs may have masked as much 47% of the global warming by greenhouse gases, with an uncertainty range of 20–80%. This presents a dilemma since efforts to curb air pollution may unmask the ABC cooling effect and enhance the surface warming. Thus efforts to reduce GHGs and air pollution should be done under one common framework. The uncertainties in our understanding of the ABC effects are large, but we are discovering new ways in which human activities are changing the climate and the environment.     

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.     

Atmospheric composition change – global and regional air quality

Air quality transcends all scales with in the atmosphere from the local to the global with handovers and feedbacks at each scale interaction. Air quality has manifold effects on health, ecosystems, heritage and climate. In this review the state of scientific understanding in relation to global and regional air quality is outlined. The review discusses air quality, in terms of emissions, processing and transport of trace gases and aerosols. New insights into the characterization of both natural and anthropogenic emissions are reviewed looking at both natural (e.g. dust and lightning) as well as plant emissions. Trends in anthropogenic emissions both by region and globally are discussed as well as biomass burning emissions. In terms of chemical processing the major air quality elements of ozone, non-methane hydrocarbons, nitrogen oxides and aerosols are covered. A number of topics are presented as a way of integrating the process view into the atmospheric context; these include the atmospheric oxidation efficiency, halogen and HO_x chemistry, nighttime chemistry, tropical chemistry, heat waves, megacities, biomass burning and the regional hot spot of the Mediterranean. New findings with respect to the transport of pollutants across the scales are discussed, in particular the move to quantify the impact of long-range transport on regional air quality. Gaps and research questions that remain intractable are identified. The review concludes with a focus of research and policy questions for the coming decade. In particular, the policy challenges for concerted air quality and climate change policy (co-benefit) are discussed.     

Status and Environmental Impact of Emissions from Thermal Power Plants in India

The main emissions from coal combustion at thermal power plants are carbon dioxide (CO₂), nitrogen oxides, sulfur oxides, chlorofluorocarbons (CFCs), and airborne inorganic particles such as fly ash and soot; CO₂, methane, and CFCs are greenhouse gases. These emissions are considered to be partially responsible for harmful global climate change. This review summarizes the status of thermal power plants in India and their various types of emissions that directly or indirectly produce harmful effects on the environment and human health. Moreover, it focuses on various types of preventive measures used to avoid/minimize emissions.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.     

Effect of climate change on air quality

Air quality is strongly dependent on weather and is therefore sensitive to climate change. Recent studies have provided estimates of this climate effect through correlations of air quality with meteorological variables, perturbation analyses in chemical transport models (CTMs), and CTM simulations driven by general circulation model (GCM) simulations of 21st-century climate change. We review these different approaches and their results. The future climate is expected to be more stagnant, due to a weaker global circulation and a decreasing frequency of mid-latitude cyclones. The observed correlation between surface ozone and temperature in polluted regions points to a detrimental effect of warming. Coupled GCM–CTM studies find that climate change alone will increase summertime surface ozone in polluted regions by 1–10 ppb over the coming decades, with the largest effects in urban areas and during pollution episodes. This climate penalty means that stronger emission controls will be needed to meet a given air quality standard. Higher water vapor in the future climate is expected to decrease the ozone background, so that pollution and background ozone have opposite sensitivities to climate change. The effect of climate change on particulate matter (PM) is more complicated and uncertain than for ozone. Precipitation frequency and mixing depth are important driving factors but projections for these variables are often unreliable. GCM–CTM studies find that climate change will affect PM concentrations in polluted environments by ±0.1–1 μg m^?3 over the coming decades. Wildfires fueled by climate change could become an increasingly important PM source. Major issues that should be addressed in future research include the ability of GCMs to simulate regional air pollution meteorology and its sensitivity to climate change, the response of natural emissions to climate change, and the atmospheric chemistry of isoprene. Research needs to be undertaken on the effect of climate change on mercury, particularly in view of the potential for a large increase in mercury soil emissions driven by increased respiration in boreal ecosystems.     

A model for NOx–O3–terpene chemistry in chamber measurements of plant gas exchange

Cuvette measurements are a tool to analyse CO₂ exchange, transipiration and deposition/emission of different trace gases by plants. To verify these experimental methods and to use them efficiently we have developed a numerical model with atmospheric chemical reactions. The model includes reactions between 54 different chemical species in the gas phase. Using the model we are able to determine optimal size/flow rate ratios and cuvette cycles (closure times) from an experimental point of view. Using the cuvette model with atmospheric chemistry more accurate estimates for emissions/deposition rates of different species can be found. Some chemical reactions are significant, e.g. for NO and terpenes, as regards the analysis and interpretation of measured concentrations. With slower flow rates through a cuvette the significance of reactions is more pronounced. However, there are some species like ozone, where stomatal deposition is a dominant phenomenon and chemistry plays a minor role.     

Reductive dechlorination of chlorofluorocarbons and hydrochlorofluorocarbons in sewage sludge and aquifer sediment microcosms

The reductive transformation of the 10 most-widely distributed fluorinated volatile compounds and of tetrachloroethene was investigated for up to 177 days under anaerobic conditions in sewage sludge and aquifer sediment slurries. Concentrations of parent compounds and of degradation products were identified by GC-MS. We observed transformation of CFC-11 to HCFC-21 and HCFC-31, of CFC-113 to HCFC-123a, chlorotrifluoroethene and trifluoroethene, of CFC-12 to HCFC-22, of HCFC-141b to HCFC-151b, and of tetrachloroethene to vinyl chloride and ethene. CFC-114, CFC-115, HCFC-142b, HFC-134a and HCFC-22 were not transformed. The results suggest that with both inocula studied here, hydrogenolysis is the primary reductive dechlorination reaction. CFC-113 was the only compound where a dichloro-elimination was observed, leading to the formation of chlorotrifluoroethene as temporal intermediate and to trifluoroethene as end product. The relative reduction rates of chlorofluoromethanes compared reasonably well with theoretical rates calculated based on thermochemical data according to the Marcus theory. Some of the accumulating HCFCs and haloethenes observed in this study are toxic and may be of practical relevance in anaerobic environments.     

Isoprene emissions and climate

Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and the carbon cycle. Isoprene is quantitatively the most important of the non-methane BVOCs (NMBVOCs), with an annual emission of about 400–600 TgC; about 90% of this is emitted by terrestrial plants. Incorporating a mechanistic treatment of isoprene emissions within land-surface schemes has recently become a focus for the modelling community, the aim being to quantify the potential magnitude of associated climate feedbacks. However, these efforts are hampered by major uncertainties about why plants emit isoprene and the relative importance of different environmental controls on isoprene emission. The availability and reliability of observations of isoprene fluxes from different types of vegetation is limited, and this also imposes constraints on model development. Nevertheless, progress is being made towards the development of mechanistic models of isoprene emission which, in conjunction with atmospheric chemistry models, will ultimately allow improved quantification of the feedbacks between the terrestrial biosphere and climate under past and future climate states.     

Modeling of ozone reactions on aircraft-related soot in the upper troposphere and lower stratosphere

Several studies in modeling atmospheric processes have suggested that heterogeneous chemistry on soot emitted from high altitude aircraft could affect stratospheric ozone depletion. However, these modeling studies were limited because they did not adequately consider the decrease in reaction probability with time as the surface of the soot becomes “poisoned” by its interactions with various gases. Here we extend UIUC's two-dimensional chemical-transport model to investigate possible effects of heterogeneous reactions of ozone on aircraft-generated carbon particles, including a treatment of soot poisoning in the model. We generally follow literature recommendations for ozone uptake probabilities and determine the available active sites on soot given partial pressures of the reactants, temperature, and time since soot emission in order to investigate ozone decrease. The regeneration of soot active sites is also taken into account in this study. We find that, even if active sites on soot surfaces are regenerated, upper troposphere and lower stratosphere ozone losses on aircraft emitted soot occurring through heterogeneous reactions are insignificant once poisoning effects are considered.     

Vertical distributions of non-methane hydrocarbons and halocarbons in the lower troposphere over northeast China

Vertical distributions of air pollutants are crucial for understanding the key processes of atmospheric transport and for evaluating chemical transport models. In this paper, we present measurements of non-methane hydrocarbons (NMHCs) and halocarbons obtained from an intensive aircraft study over northeast (NE) China in summer 2007. Most compounds exhibited a typical negative profile of decreasing mixing ratios with increasing altitude, although the gradients differed with different species. Three regional plumes with enhanced VOC mixing ratios were discerned and characterized. An aged plume transported from the northern part of the densely populated North China Plain (NCP; i.e. Beijing–Tianjin area) showed relatively higher levels of HCFC-22, 1,2-dichloroethane (1,2-DCE) and toluene. In comparison, the plume originating from Korea had higher abundances of CFC-12, tetrachloroethene (C₂Cl₄) and methyl chloride (CH₃Cl), while regional air masses from NE China contained more abundant light alkanes. By comparing these results with the earlier PEM-West B (1994) and TRACE-P (2001) aircraft measurements, continuing declining trends were derived for methyl chloroform (CH₃CCl₃), tetrachloromethane (CCl₄) and C₂Cl₄ over the greater China–northwestern Pacific region, indicating the accomplishment of China in reducing these compounds under the Montreal protocol. However, the study also provided evidence for the continuing emissions of several halocarbons in China in 2007, such as CFCs (mainly from materials in stock) and HCFCs.     

Observed trends for CF3-containing compounds in background air at Cape Meares, Oregon, Point Barrow, Alaska, and Palmer Station, Antarctica

The concentrations of CF(3)-containing compounds in archived air samples collected at Cape Meares, Oregon, from 1978 to 1997, at Point Barrow, Alaska, from 1995 to 1998, and at Palmer Station, Antarctica, from 1991 to 1997, were determined by high resolution gas chromatography and high resolution mass spectrometry. The CF(3)-containing compounds measured by this method and discussed here are: the perfluorinated compound, C(3)F(8) (FC 218); four perhalogenated compounds, CF(3)Cl (CFC 13), CF(3)CF(2)Cl (CFC 115), CF(3)CFCl(2) (CFC 114a), and CF(3)Br (Halon 1301); and three hydrofluorocompounds, CF(3)H (HFC 23), CF(3)CH(3) (HFC 143a), and CF(3)CH(2)F (HFC 134a). For four of these compounds, very few measurements have been previously reported. The atmospheric concentrations of all of the CF(3)-containing compounds continuously increased in time over the sample collection periods. From these data, the annual rates of emission into the atmosphere have been estimated. The emission rates fall into one of three distinct categories. The annual emission rates of C(3)F(8), CF(3)H, CF(3)CH(3), and CF(3)CH(2)F have continuously increased over the last two decades. That of CF(3)CFCl(2) has decreased continuously. Emission rates for CF(3)Cl, CF(3)CF(2)Cl, and CF(3)Br reached maximum levels in the late 1980s, and have been decreasing in the 1990s. The emission rates of C(3)F(8), CF(3)CH(3) and CF(3)CH(2)F were nearly zero 20 years ago but have increased rapidly during the last decade.