A. McCulloch

A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE

We describe in detail the instrumentation and calibrations used in the Atmospheric Lifetime Experiment (ALE), the Global Atmospheric Gases Experiment (GAGE), and the Advanced Global Atmospheric Gases Experiment (AGAGE) and present a history of the majority of the anthropogenic ozone-depleting and climate-forcing gases in air based on these experiments. Beginning in 1978, these three successive automated high-frequency in situ experiments have documented the long-term behavior of the measured concentrations of these gases over the past 20 years, and show both the evolution of latitudinal gradients and the high-frequency variability due to sources and circulation. We provide estimates of the long-term trends in total chlorine contained in long-lived halocarbons involved in ozone depletion. We summarize interpretations of these measurements using inverse methods to determine trace gas lifetimes and emissions. Finally, we provide a combined observational and modeled reconstruction of the evolution of chlorocarbons by latitude in the atmosphere over the past 60 years which can be used as boundary conditions for interpreting trapped air in glaciers and oceanic measurements of chlorocarbon tracers of the deep oceanic circulation. Some specific conclusions are as follows: (1) International compliance with the Montreal Protocol is so far resulting in chlorofluorocarbon and chlorocarbon mole fractions comparable to target levels; (2) mole fractions of total chlorine contained in long-lived halocarbons (CCl 2 F 2 , CCl 3 F, CH 3 CCl 3 , CCl 4 , CHClF 2 , CCl 2 FCClF 2 , CH 3 Cl, CH 2 Cl 2 , CHCl 3 , CCl 2 =CCl 2 ) in the lower troposphere reached maximum values of about 3.6 ppb in 1993 and are beginning to slowly decrease in the global lower atmosphere; (3) the chlorofluorocarbons have atmospheric lifetimes consistent with destruction in the stratosphere being their principal removal mechanism; (4) multiannual variations in chlorofluorocarbon and chlorocarbon emissions deduced from ALE/GAGE/AGAGE data are consistent approximately with variations estimated independently from industrial production and sales data where available (CCl 2 F 2 (CFC-12) and CCl 2 FCClF 2 (CFC-113) show the greatest discrepancies); (5) the mole fractions of the hydrochlorofluorocarbons and hydrofluorocarbons, which are replacing the regulated halocarbons, are rising very rapidly in the atmosphere, but with the exception of the much longer manufactured CHClF 2 (HCFC-22), they are not yet at levels sufficient to contribute significantly to atmospheric chlorine loading. These replacement species could in the future provide independent estimates of the global weighted-average OH concentration provided their industrial emissions are accurately documented; (6) in the future, analysis of pollution events measured using high-frequency in situ measurements of chlorofluorocarbons and their replacements may enable emission estimates at the regional level, which, together with industrial end-use data, are of sufficient accuracy to be capable of identifying regional noncompliance with the Montreal Protocol.

Composite global emissions of reactive chlorine from anthropogenic and natural sources: Reactive Chlorine Emissions Inventory

Emission inventories for major reactive tropospheric CI species (particulate CI, HC1, C1NO2, CH3CI, CHCI3, CH3CCI3, C2C14, C2HC13, CH2C12, and CHCIF2) were integrated across source types (terrestrial biogenic and oceanic emissions, sea-salt production and dechlorination, biomass burning, industrial emissions, fossil-fuel combustion, and incinera- tion). Composite emissions were compared with known sinks to assess budget closure; relative contributions of natural and anthropogenic sources were differentiated. Model cal- culations suggest that conventional acid-displacement reactions involving Sov)+O3, S(Iv)+ H202, and H2SO4 and HNO3 scavenging account for minor fractions of sea-salt dechlorina- tion globally. Other important chemical pathways involving sea-salt aerosol apparently pro- duce most volatile chlorine in the troposphere. The combined emissions of CH3CI from known sources account for about half of the modeled sink, suggesting fluxes from known sources were unde:estimated, the OH sink was overestimated, or significant unidentified sources exist. Anthropogenic activities (primarily biomass burning) contribute about half the net CH3CI emitted from known sources. Anthropogenic emissions account for only about 10% of the modeled CHCl3 sink. Although poorly constrained, significant fractions of tropo- spheric CH2C12 (25%), C2HC13 (10%), and C2C14 (5%) are emitted from the surface ocean; the combined contributions of C2C14 and C2HC13 from all natural sources may be substan- tially higher than the estimated oceanic flux.

Global emissions of hydrogen chloride and chloromethane from coal combustion, incineration and industrial activities: Reactive Chlorine Emissions Inventory

Much if not all of the chlorine present in fossil fuels is released into the atmosphere as hydrogen chloride (HCl) and chloromethane (CH3Cl, methyl chloride). The chlorine content of oil-based fuels is so low that these sources can be neglected, but coal combustion provides significant releases. On the basis of national statistics for the quantity and quality of coal burned during 1990 in power and heat generation, industrial conversion and residential and commercial heating, coupled with information on the chlorine contents of coals, a global inventory of national HCl emissions from this source has been constructed. This was combined with an estimate of the national emissions of HCl from waste combustion (both large-scale incineration and trash burning) which was based on an estimate of the global quantity released from this source expressed per head of population. Account was taken of reduced emissions where flue gases were processed, for example to remove sulphur dioxide. The HCl emitted in 1990, comprising 4.6 ± 4.3 Tg Cl from fossil fuel and 2 ± 1.9 Tg Cl from waste burning, was spatially distributed using available information on point sources such as power generation utilities and population density by default. Also associated with these combustion sources are chloromethane emissions, calculated to be 0.075 ± 0.07 Tg as Cl (equivalent) from fossil fuels and 0.032 ± 0.023 Tg Cl (equivalent) from waste combustion. These were distributed spatially exactly as the HCl emissions, and a further 0.007 Tg Cl in chloromethane from industrial process activity was distributed by point sources.

Long-term trends in concentrations of halocarbons and radiatively active trace gases in atlantic and european air masses monitored at mace head, Ireland from 1987–1994

Long-term trends in trace gas concentrations over the period 1987–1994 are reported here for air masses advected to the Mace Head monitoring station on the remote west coast of Ireland. The trace gases covered include the principal halocarbons: CFC-11, CFC-12, CFC-113, CCl4 and methyl chloroform; the radiatively active trace gases: carbon dioxide, methane, nitrous oxide and ozone; together with carbon monoxide, the major photochemical ozone precursor. By careful sorting using two independent techniques, it is possible to distinguish air masses that arrive at Mace Head from over the North Atlantic Ocean and those that have recently travelled over polluted European continental land areas. Concentration trends have been derived for each trace gas in polluted European continental and baseline North Atlantic maritime air and they appear to be distinctly different. Using a simple long-range transport model, estimates have been made of the European source strengths required to sustain the observed concentrations of each trace gas and their recent trends. These are compared with published emission inventories where they are available. The European continent appears to be a significant source of methane, carbon dioxide and nitrous oxide, a net sink for ozone and a declining source of the principal halocarbons and carbon monoxide.

Industrial emissions of trichloroethene, tetrachloroethene, and dichloromethane: Reactive Chlorine Emissions Inventory

The identified emissions of the title compounds come predominantly from their use in industrial and commercial processes. Trichloroethene and tetrachloroethene have also been found as byproducts of gasoline and coal combustion; these sources were also considered but shown to be insignificant compared with industrial releases. Global emissions during 1990, amounting to 0.241±0.013 Tg of trichloroethene, 0.366±0.020 Tg of tetrachloroethene, and 0.583±0.032 Tg of dichloromethane (0.195±0.010, 0.313±0.017, and 0.487±0.027 Tg as chlorine, respectively) have been assigned to individual countries and thence to a 1° latitude × 1° longitude grid based on a combination of three data sets: regional sales data that were available on a continental scale; economic activity in the form of national Gross Domestic Products; and the population distribution within each country. For those countries where they were available, data for the quantities and locations of reported emissions were also incorporated. Uncertainty in the distributed emissions is ±4% relative to countries with the largest emissions. The results, which are complementary to the marine fluxes and releases from biomass burning reported by Khalil et al [this issue] and Lobert et al [this issue], respectively, are recorded here as maps and are also available from the Global Emissions Inventory Activity web site at http://groundhog.sprl.umich.edu/geia/rcei. While the industrial regions of North America, Europe, and Japan are the largest sites of anthropogenic emissions, there are also significant sources in the developing nations of Asia; in contrast, anthropogenic emissions within the southern hemisphere are much smaller and more widely dispersed. The total emissions of dichloromethane appear to match the observed atmospheric concentrations, but about 25% of the flux of tetrachloroethene calculated from observations remains unaccounted, and significant extra emissions of trichloroethene are necessary to effect a balance. The known sources have been examined thoroughly in this work, and so it is reasonably certain that the additional emissions are not a deliberate result of human activity; however, there is no means of discriminating their origin unequivocally, and the missing quantities may be inadvertent byproducts of anthropogenic activities.

The production and global distribution of emissions of trichloroethene, tetrachloroethene and dichloromethane over the period 1988–1992

Abstract Emissions of trichloroethene, tetrachloroethene and dichloromethane have been estimated from audited production and sales data provided by members of trade associations in U.S.A., Japan and Europe. Together with an estimate of production and use in the former centrally planned economies, these comprise global data. In addition to the annual information, monthly data were collected for one compound: dichloromethane. These showed that there was no significant seasonal component to the emissions, either globally or when they were subdivided into regions or categories of end use. It is assumed that the other solvents show similar behaviour. The emissions were estimated in six geographical regions: North America, Europe, the Far East, the Northern Hemisphere tropics, the rest of the Northern Hemisphere and the whole of the Southern Hemisphere. Atmospheric concentrations calculated from the emissions of tetrachloroethene and dichloromethane are broadly consistent with observations, with some interesting differences which merit further investigation of potential additional sources and sinks. On the other hand, the calculated atmospheric concentration of trichloroethene is very much less than that observed, suggesting a significant additional global source of this compound.

Global trends, seasonal cycles and European emissions of dichloromethane, trichloroethene and tetrachloroethene from the AGAGE observations at Mace Head, Ireland and Cape Grim, Tasmania

[1] In situ observations (every 4 hours) of dichloromethane (CH 2 Cl 2 ) from April 1995 to December 2004 and trichloroethene (C 2 HCl 3 ) and tetrachloroethene (C 2 Cl 4 ) from September 2000 to December 2004 are reported for the Advanced Global Atmospheric Gases Experiment (AGAGE) station at Mace Head, Ireland. At a second AGAGE station at Cape Grim, Tasmania, CH 2 Cl 2 and C 2 Cl 4 data collection commenced in 1998 and 2000, respectively. C 2 HCl 3 is below the limit of detection at Cape Grim except during pollution episodes. At Mace Head CH 2 Cl 2 shows a downward trend from 1995 to 2004 of 0.7±0.2 ppt yr -1 (ppt: expressed as dry mole fractions in 10 12 ), although from 1998 to 2004 the decrease has been only 0.3 ± 0.1ppt yr -1 . Conversely, there has been a small but significant growth of 0.05 ± 0.01 ppt yr -1 in CH 2 Cl 2 at Cape Grim. The time series for C 2 HCl 3 and C 2 Cl 4 are relatively short for accurate trend analyses; however, we observe a small but significant decline in C 2 Cl 4 (0.18 ± 0.05 ppt yr -1 ) at Mace Head. European emissions inferred from AGAGE measurements are compared to recent estimates from industry data and show general agreement for C 2 HCl 3 . Emissions estimated from observations are lower than industry emission estimates for C 2 Cl 4 and much lower in the case of CH 2 Cl 2 . A study of wildfires in Tasmania, uncontaminated by urban emissions, suggests that the biomass burning source of CH 2 Cl 2 may have been previously overestimated. All three solvents have distinct annual cycles, with the phases and amplitudes reflecting their different chemical reactivity with OH as the primary sink.

Growth of fluoroform (CHF3, HFC‐23) in the background atmosphere

There is growing concern over the emission and accumulation of very long-lived fluorinated trace gases in the atmosphere, due to their large global warming potentials (GWPs). Unlike CFCs and other ozone-depleting, chlorinated and brominated chemicals, consumption of these fluorinated compounds is not controlled by the Montreal Protocol or any other international agreement. Of all the known and potential trace ‘greenhouse’ gases, the two with the highest GWPs are sulfur hexafluoride (SF6) and fluoroform (CHF3, HFC-23). Whereas several studies have reported the detection and accumulation of SF6 in the atmosphere, the presence of HFC-23 has remained unreported. We have found that present-day HFC-23 concentrations (c. 11 pptv in late 1995) exceed those of SF6 by a factor of three. Concentrations have steadily increased in the atmosphere since at least 1978, and are continuing to do so at a present rate of 5% per year. Furthermore, HFC-23 appears to be long-lived in the atmosphere, with a stratospheric lifetime of at least 1000 years, and a modelled tropospheric lifetime of 230 years. In terms of global warming, the cumulative emissions of HFC-23 up to, and including, 1995 are equivalent to 1.6 billion tonnes of CO2.

CFC and Halon replacements in the environment

Abstract Substitute fluorocarbons may have direct environmental impact, for example as greenhouse gases, or indirect impacts through the products of their decomposition in the environment. The mechanisms of that atmospheric decomposition are reviewed here and shown to be well established now. The end products are halogen acids and trifluoroacetic acid, all of which pre-exist in the environment in quantities greater than are expected to arise from fluorocarbon use and emissions. Furthermore, the growth in use of fluorocarbon replacements has been shown to be far less than the fall in CFC and Halon production. Hydrochlorofluorocarbons (HCFCs) have replaced less than one third of CFCs and are, themselves, ozone depleting substances that will be phased out under the Montreal Protocol. The growth in hydrofluorocarbons (HFCs) amounts to about 10% of the fall in CFCs. It is likely that the impact of new fluorocarbons on climate change will be a very small fraction of the total impact, which comes mainly from the accumulation of carbon dioxide in the atmosphere.

Low European methyl chloroform emissions inferred from long-term atmospheric measurements

Methyl chloroform (CH3CCl3, 1,1,1,-trichloroethane) was used widely as a solvent before it was recognized to be an ozone-depleting substance and its phase-out was introduced under the Montreal Protocol. Subsequently, its atmospheric concentration has declined steadily and recent European methyl chloroform consumption and emissions were estimated to be less than 0.1 gigagrams per year. However, data from a short-term tropospheric measurement campaign (EXPORT) indicated that European methyl chloroform emissions could have been over 20 gigagrams in 2000 (ref. 6), almost doubling previously estimated global emissions. Such enhanced emissions would significantly affect results from the CH3CC13 method of deriving global abundances of hydroxyl radicals (OH) (refs 7–12)—the dominant reactive atmospheric chemical for removing trace gases related to air pollution, ozone depletion and the greenhouse effect. Here we use long-term, high-frequency data from Mace Head, Ireland and Jungfraujoch, Switzerland, to infer European methyl chloroform emissions. We find that European emission estimates declined from about 60 gigagrams per year in the mid-1990s to 0.3–1.4 and 1.9–3.4 gigagrams per year in 2000–03, based on Mace Head and Jungfraujoch data, respectively. Our European methyl chloroform emission estimates are therefore higher than calculated from consumption data, but are considerably lower than those derived from the EXPORT campaign in 2000 (ref. 6).