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Reimann, S, Elkins JW, Fraser PJ, Hall BD, Kurylo MJ, Mahieu E, Montzka SA, Prinn RG, Rigby M, Simmonds PG, Weiss RF.  2018.  Observing the atmospheric evolution of ozone-depleting substances. Comptes Rendus Geoscience. 350:384-392.   10.1016/j.crte.2018.08.008   AbstractWebsite

The atmospheric observations of ozone-depleting substances (ODSs) have been essential for following their atmospheric response to the production and use restrictions imposed by the Montreal Protocol and its Amendments and Adjustments. ODSs have been used since the first half of the 20th century in industrial and domestic applications. However, their atmospheric growth went unnoticed until the early 1970s, when they were discovered using gas chromatograph-electron capture detection (GC-ECD) instruments. Similar instrumentation formed the basis of global flask and in situ measurements commenced by NOAA and ALE/GAGE/AGAGE in the late 1970s. The combination of these networks, supported by a number of other laboratories, has been essential for following the tropospheric trends of ODSs. Additionally, ground-based remote sensing measurements within NDACC and aircraft-based observation programs have been crucial for measuring the evolution of the ODS abundances over the entire atmosphere. Maintaining these networks at least at their current state is vital for ensuring the on-going verification of the success of the Montreal Protocol. (C) 2018 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Simmonds, PG, Rigby M, McCulloch A, Vollmer MK, Henne S, Muhle J, O'Doherty S, Manning AJ, Krummel PB, Fraser PJ, Young D, Weiss RF, Salameh PK, Harth CM, Reimann S, Trudinger CM, Steele LP, Wang RHJ, Ivy DJ, Prinn RG, Mitrevski B, Etheridge DM.  2018.  Recent increases in the atmospheric growth rate and emissions of HFC-23 (CHF3) and the link to HCFC-22 (CHClF2) production. Atmospheric Chemistry and Physics. 18:4153-4169.   10.5194/acp-18-4153-2018   AbstractWebsite

High frequency measurements of trifluoromethane (HFC-23, CHF3), a potent hydrofluorocarbon greenhouse gas, largely emitted to the atmosphere as a by-product of the production of the hydrochlorofluorocarbon HCFC-22 (CHClF2), at five core stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, combined with measurements on firn air, old Northern Hemisphere air samples and Cape Grim Air Archive (CGAA) air samples, are used to explore the current and historic changes in the atmospheric abundance of HFC-23. These measurements are used in combination with the AGAGE 2-D atmospheric 12-box model and a Bayesian inversion methodology to determine model atmospheric mole fractions and the history of global HFC-23 emissions. The global modelled annual mole fraction of HFC-23 in the background atmosphere was 28.9 +/- 0.6 pmol mol(-1) at the end of 2016, representing a 28% increase from 22.6 +/- 0.4 pmol mol(-1) in 2009. Over the same time frame, the modelled mole fraction of HCFC-22 increased by 19% from 199 +/- 2 to 237 +/- 2 pmol mol(-1). However, unlike HFC-23, the annual average HCFC-22 growth rate slowed from 2009 to 2016 at an annual average rate of -0.5 pmol mol(-1) yr(-2). This slowing atmospheric growth is consistent with HCFC-22 moving from dispersive (high fractional emissions) to feedstock (low fractional emissions) uses, with HFC-23 emissions remaining as a consequence of incomplete mitigation from all HCFC-22 production. Our results demonstrate that, following a minimum in HFC-23 global emissions in 2009 of 9.6 +/- 0.6, emissions increased to a maximum in 2014 of 14.5 +/- 0.6 Gg yr(-1) and then declined to 12.7 +/- 0.6 Gg yr(-1) (157 MtCO(2) eq.yr(-1)) in 2016. The 2009 emissions minimum is consistent with estimates based on national reports and is likely a response to the implementation of the Clean Development Mechanism (CDM) to mitigate HFC-23 emissions by incineration in developing (non-Annex 1) countries under the Kyoto Protocol. Our derived cumulative emissions of HFC-23 during 20102016 were 89 +/- 2 Gg (1.1 +/- 0.2 GtCO(2) eq.), which led to an increase in radiative forcing of 1.0 +/- 0.1mWm(-2) over the same period. Although the CDM had reduced global HFC-23 emissions, it cannot now offset the higher emissions from increasing HCFC-22 production in non-Annex 1 countries, as the CDM was closed to new entrants in 2009. We also find that the cumulative European HFC-23 emissions from 2010 to 2016 were similar to 1.3 Gg, corresponding to just 1.5% of cumulative global HFC-23 emissions over this same period. The majority of the increase in global HFC-23 emissions since 2010 is attributed to a delay in the adoption of mitigation technologies, predominantly in China and East Asia. However, a reduction in emissions is anticipated, when the Kigali 2016 amendment to the Montreal Protocol, requiring HCFC and HFC production facilities to introduce destruction of HFC-23, is fully implemented.

Xiang, B, Patra PK, Montzka SA, Miller SM, Elkins JW, Moore FL, Atlas EL, Miller BR, Weiss RF, Prinn RG, Wofsy SC.  2014.  Global emissions of refrigerants HCFC-22 and HFC-134a: Unforeseen seasonal contributions. Proceedings of the National Academy of Sciences of the United States of America. 111:17379-17384.   10.1073/pnas.1417372111   AbstractWebsite

HCFC-22 (CHClF2) and HFC-134a (CH2FCF3) are two major gases currently used worldwide in domestic and commercial refrigeration and air conditioning. HCFC-22 contributes to stratospheric ozone depletion, and both species are potent greenhouse gases. In this work, we study in situ observations of HCFC-22 and HFC-134a taken from research aircraft over the Pacific Ocean in a 3-y span [Hlaper-Pole-to-Pole Observations (HIPPO) 2009-2011] and combine these data with long-term ground observations from global surface sites [ National Oceanic and Atmospheric Administration (NOAA) and Advanced Global Atmospheric Gases Experiment (AGAGE) networks]. We find the global annual emissions of HCFC-22 and HFC-134a have increased substantially over the past two decades. Emissions of HFC-134a are consistently higher compared with the United Nations Framework Convention on Climate Change (UNFCCC) inventory since 2000, by 60% more in recent years (2009-2012). Apart from these decadal emission constraints, we also quantify recent seasonal emission patterns showing that summertime emissions of HCFC-22 and HFC-134a are two to three times higher than wintertime emissions. This unforeseen large seasonal variation indicates that unaccounted mechanisms controlling refrigerant gas emissions are missing in the existing inventory estimates. Possible mechanisms enhancing refrigerant losses in summer are (i) higher vapor pressure in the sealed compartment of the system at summer high temperatures and (ii) more frequent use and service of refrigerators and air conditioners in summer months. Our results suggest that engineering (e. g., better temperature/vibration-resistant system sealing and new system design of more compact/efficient components) and regulatory (e. g., reinforcing system service regulations) steps to improve containment of these gases from working devices could effectively reduce their release to the atmosphere.

Thompson, RL, Patra PK, Ishijima K, Saikawa E, Corazza M, Karstens U, Wilson C, Bergamaschi P, Dlugokencky E, Sweeney C, Prinn RG, Weiss RF, O'Doherty S, Fraser PJ, Steele LP, Krummel PB, Saunois M, Chipperfield M, Bousquet P.  2014.  TransCom N2O model inter-comparison - Part 1: Assessing the influence of transport and surface fluxes on tropospheric N2O variability. Atmospheric Chemistry and Physics. 14:4349-4368.   10.5194/acp-14-4349-2014   AbstractWebsite

We present a comparison of chemistry-transport models (TransCom-N2O) to examine the importance of atmospheric transport and surface fluxes on the variability of N2O mixing ratios in the troposphere. Six different models and two model variants participated in the inter-comparison and simulations were made for the period 2006 to 2009. In addition to N2O, simulations of CFC-12 and SF6 were made by a subset of four of the models to provide information on the models' proficiency in stratosphere-troposphere exchange (STE) and meridional transport, respectively. The same prior emissions were used by all models to restrict differences among models to transport and chemistry alone. Four different N2O flux scenarios totalling between 14 and 17 TgN yr(-1) (for 2005) globally were also compared. The modelled N2O mixing ratios were assessed against observations from in situ stations, discrete air sampling networks and aircraft. All models adequately captured the large-scale patterns of N2O and the vertical gradient from the troposphere to the stratosphere and most models also adequately captured the N2O tropospheric growth rate. However, all models underestimated the inter-hemispheric N2O gradient by at least 0.33 parts per billion (ppb), equivalent to 1.5 TgN, which, even after accounting for an overestimate of emissions in the Southern Ocean of circa 1.0 TgN, points to a likely underestimate of the Northern Hemisphere source by up to 0.5 TgN and/or an overestimate of STE in the Northern Hemisphere. Comparison with aircraft data reveal that the models over-estimate the amplitude of the N2O seasonal cycle at Hawaii (21 degrees N, 158 degrees W) below circa 6000 m, suggesting an overestimate of the importance of stratosphere to troposphere transport in the lower troposphere at this latitude. In the Northern Hemisphere, most of the models that provided CFC-12 simulations captured the phase of the CFC-12, seasonal cycle, indicating a reasonable representation of the timing of STE. However, for N2O all models simulated a too early minimum by 2 to 3 months owing to errors in the seasonal cycle in the prior soil emissions, which was not adequately represented by the terrestrial biosphere model. In the Southern Hemisphere, most models failed to capture the N2O and CFC-12 seasonality at Cape Grim, Tasmania, and all failed at the South Pole, whereas for SF6, all models could capture the seasonality at all sites, suggesting that there are large errors in modelled vertical transport in high southern latitudes.

Simmonds, PG, Manning AJ, Athanassiadou M, Scaife AA, Derwent RG, O'Doherty S, Harth CM, Weiss RF, Dutton GS, Hall BD, Sweeney C, Elkins JW.  2013.  Interannual fluctuations in the seasonal cycle of nitrous oxide and chlorofluorocarbons due to the Brewer-Dobson circulation. Journal of Geophysical Research-Atmospheres. 118:10694-10706.   10.1002/jgrd.50832   AbstractWebsite

The tropospheric seasonal cycles of N2O, CFC-11 (CCl3F), and CFC-12 (CCl2F2) are influenced by atmospheric dynamics. The interannually varying summertime minima in mole fractions of these trace gases have been attributed to interannual variations in mixing of stratospheric air (depleted in CFCs and N2O) with tropospheric air with a few months lag. The amount of wave activity that drives the stratospheric circulation and influences the winter stratospheric jet and subsequent mass transport across the tropopause appears to be the primary cause of this interannual variability. We relate the observed seasonal minima of species at three Northern Hemisphere sites (Mace Head, Ireland; Trinidad Head, U.S.; and Barrow, Alaska) with the behavior of the winter stratospheric jet. As a result, a good correlation is obtained between zonal winds in winter at 10 hPa, 58°N–68°N, and the detrended seasonal minima in the stratosphere-influenced tracers. For these three tracers, individual Pearson correlation coefficients (r) between 0.51 and 0.71 were found, with overall correlations of between 0.67 and 0.77 when “composite species” were considered. Finally, we note that the long-term observations of CFCs and N2O in the troposphere provide an independent monitoring method complementary to satellite data. Furthermore, they could provide a useful observational measure of the strength of stratosphere-troposphere exchange and, thus, could be used to monitor any long-term trend in the Brewer-Dobson circulation which is predicted by climate models to increase over the coming decades.

Ivy, DJ, Arnold T, Harth CM, Steele LP, Muhle J, Rigby M, Salameh PK, Leist M, Krummel PB, Fraser PJ, Weiss RF, Prinn RG.  2012.  Atmospheric histories and growth trends of C4F10, C5F12, C6F14, C7F16 and C8F18. Atmospheric Chemistry and Physics. 12:4313-4325.   10.5194/acp-12-4313-2012   AbstractWebsite

Atmospheric observations and trends are presented for the high molecular weight perfluorocarbons (PFCs): decafluorobutane (C4F10), dodecafluoropentane (C5F12), tetradecafluorohexane (C6F14), hexadecafluoroheptane (C7F16) and octadecafluorooctane (C8F18). Their atmospheric histories are based on measurements of 36 Northern Hemisphere and 46 Southern Hemisphere archived air samples collected between 1973 to 2011 using the Advanced Global Atmospheric Gases Experiment (AGAGE) 'Medusa' preconcentration gas chromatography-mass spectrometry systems. A new calibration scale was prepared for each PFC, with estimated accuracies of 6.8% for C4F10, 7.8% for C5F12, 4.0% for C6F14, 6.6% for C7F16 and 7.9% for C8F18. Based on our observations the 2011 globally averaged dry air mole fractions of these heavy PFCs are: 0.17 parts-per-trillion (ppt, i.e., parts per 10(12)) for C4F10, 0.12 ppt for C5F12, 0.27 ppt for C6F14, 0.12 ppt for C7F16 and 0.09 ppt for C8F18. These atmospheric mole fractions combine to contribute to a global average radiative forcing of 0.35 mW m(-2), which is 6% of the total anthropogenic PFC radiative forcing (Montzka and Reimann, 2011; Oram et al., 2012). The growth rates of the heavy perfluorocarbons were largest in the late 1990s peaking at 6.2 parts per quadrillion (ppq, i.e., parts per 10(15)) per year (yr) for C4F10, at 5.0 ppq yr(-1) for C5F12 and 16.6 ppq yr(-1) for C6F14 and in the early 1990s for C7F16 at 4.7 ppq yr(-1) and in the mid 1990s for C8F18 at 4.8 ppq yr(-1). The 2011 globally averaged mean atmospheric growth rates of these PFCs are subsequently lower at 2.2 ppq yr(-1) for C4F10, 1.4 ppq yr(-1) for C5F12, 5.0 ppq yr(-1) for C6F14, 3.4 ppq yr(-1) for C7F16 and 0.9 ppq yr(-1) for C8F18. The more recent slowdown in the growth rates suggests that emissions are declining as compared to the 1980s and 1990s.

Nevison, CD, Dlugokencky E, Dutton G, Elkins JW, Fraser P, Hall B, Krummel PB, Langenfelds RL, O'Doherty S, Prinn RG, Steele LP, Weiss RF.  2011.  Exploring causes of interannual variability in the seasonal cycles of tropospheric nitrous oxide. Atmospheric Chemistry and Physics. 11:3713-3730.   10.5194/acp-11-3713-2011   AbstractWebsite

Seasonal cycles in the mixing ratios of tropospheric nitrous oxide (N(2)O) are derived by detrending long-term measurements made at sites across four global surface monitoring networks. The detrended monthly data display large interannual variability, which at some sites challenges the concept of a "mean" seasonal cycle. In the Northern Hemisphere, correlations between polar winter lower stratospheric temperature and detrended N(2)O data, around the month of the seasonal minimum, provide empirical evidence for a stratospheric influence, which varies in strength from year to year and can explain much of the interannual variability in the surface seasonal cycle. Even at sites where a strong, competing, regional N(2)O source exists, such as from coastal upwelling at Trinidad Head, California, the stratospheric influence must be understood to interpret the biogeochemical signal in monthly mean data. In the Southern Hemisphere, detrended surface N(2)O monthly means are correlated with polar spring lower stratospheric temperature in months preceding the N(2)O minimum, providing empirical evidence for a coherent stratospheric influence in that hemisphere as well, in contrast to some recent atmospheric chemical transport model (ACTM) results. Correlations between the phasing of the surface N(2)O seasonal cycle in both hemispheres and both polar lower stratospheric temperature and polar vortex break-up date provide additional support for a stratospheric influence. The correlations discussed above are generally more evident in high-frequency in situ data than in data from weekly flask samples. Furthermore, the interannual variability in the N(2)O seasonal cycle is not always correlated among in situ and flask networks that share common sites, nor do the mean seasonal amplitudes always agree. The importance of abiotic influences such as the stratospheric influx and tropospheric transport on N(2)O seasonal cycles suggests that, at sites remote from local sources, surface N(2)O mixing ratio data by themselves are unlikely to provide information about seasonality in surface sources, e. g., for atmospheric inversions, unless the ACTMs employed in the inversions accurately account for these influences. An additional abioitc influence is the seasonal ingassing and outgassing of cooling and warming surface waters, which creates a thermal signal in tropospheric N(2)O that is of particular importance in the extratropical Southern Hemisphere, where it competes with the biological ocean source signal.

Xiao, X, Prinn RG, Fraser PJ, Weiss RF, Simmonds PG, O'Doherty S, Miller BR, Salameh PK, Harth CM, Krummel PB, Golombek A, Porter LW, Butler JH, Elkins JW, Dutton GS, Hall BD, Steele LP, Wang RHJ, Cunnold DM.  2010.  Atmospheric three-dimensional inverse modeling of regional industrial emissions and global oceanic uptake of carbon tetrachloride. Atmospheric Chemistry and Physics. 10:10421-10434.   10.5194/acp-10-10421-2010   AbstractWebsite

Carbon tetrachloride (CCl(4)) has substantial stratospheric ozone depletion potential and its consumption is controlled under the Montreal Protocol and its amendments. We implement a Kalman filter using atmospheric CCl(4) measurements and a 3-dimensional chemical transport model to estimate the interannual regional industrial emissions and seasonal global oceanic uptake of CCl(4) for the period of 1996-2004. The Model of Atmospheric Transport and Chemistry (MATCH), driven by offline National Center for Environmental Prediction (NCEP) reanalysis meteorological fields, is used to simulate CCl(4) mole fractions and calculate their sensitivities to regional sources and sinks using a finite difference approach. High frequency observations from the Advanced Global Atmospheric Gases Experiment (AGAGE) and the Earth System Research Laboratory (ESRL) of the National Oceanic and Atmospheric Administration (NOAA) and low frequency flask observations are together used to constrain the source and sink magnitudes, estimated as factors that multiply the a priori fluxes. Although industry data imply that the global industrial emissions were substantially declining with large interannual variations, the optimized results show only small interannual variations and a small decreasing trend. The global surface CCl(4) mole fractions were declining in this period because the CCl(4) oceanic and stratospheric sinks exceeded the industrial emissions. Compared to the a priori values, the inversion results indicate substantial increases in industrial emissions originating from the South Asian/Indian and Southeast Asian regions, and significant decreases in emissions from the European and North American regions.

Miller, BR, Rigby M, Kuijpers LJM, Krummel PB, Steele LP, Leist M, Fraser PJ, McCulloch A, Harth C, Salameh P, Muhle J, Weiss RF, Prinn RG, Wang RHJ, O'Doherty S, Greally BR, Simmonds PG.  2010.  HFC-23 (CHF3) emission trend response to HCFC-22 (CHClF2) production and recent HFC-23 emission abatement measures. Atmospheric Chemistry and Physics. 10:7875-7890.   10.5194/acp-10-7875-2010   AbstractWebsite

HFC-23 (also known as CHF(3), fluoroform or trifluoromethane) is a potent greenhouse gas (GHG), with a global warming potential (GWP) of 14 800 for a 100-year time horizon. It is an unavoidable by-product of HCFC-22 (CHClF(2), chlorodifluoromethane) production. HCFC-22, an ozone depleting substance (ODS), is used extensively in commercial refrigeration and air conditioning, in the extruded polystyrene (XPS) foam industries (dispersive applications) and also as a feedstock in fluoropolymer manufacture (a non-dispersive use). Aside from small markets in specialty uses, HFC-23 has historically been considered a waste gas that was, and often still is, simply vented to the atmosphere. Efforts have been made in the past two decades to reduce HFC-23 emissions, including destruction (incineration) in facilities in developing countries under the United Nations Framework Convention on Climate Change's (UNFCCC) Clean Development Mechanism (CDM), and by process optimization and/or voluntary incineration by most producers in developed countries. We present observations of lower-tropospheric mole fractions of HFC-23 measured by 'Medusa' GC/MSD instruments from ambient air sampled in situ at the Advanced Global Atmospheric Gases Experiment (AGAGE) network of five remote sites (2007-2009) and in Cape Grim air archive (CGAA) samples (1978-2009) from Tasmania, Australia. These observations are used with the AGAGE 2-D atmospheric 12-box model and an inverse method to produce model mole fractions and a 'top-down' HFC-23 emission history. The model 2009 annual mean global lower-tropospheric background abundance is 22.6 (+/- 0.2) pmol mol(-1). The derived HFC-23 emissions show a 'plateau' during 1997-2003, followed by a rapid similar to 50% increase to a peak of 15.0 (+1.3/-1.2) Gg/yr in 2006. Following this peak, emissions of HFC-23 declined rapidly to 8.6 (+0.9/-1.0) Gg/yr in 2009, the lowest annual emission of the past 15 years. We derive a 1990-2008 'bottom-up' HFC-23 emission history using data from the United Nations Environment Programme and the UNFCCC. Comparison with the top-down HFC-23 emission history shows agreement within the stated uncertainties. In the 1990s, HFC-23 emissions from developed countries dominated all other sources, then began to decline and eventually became fairly constant during 2003-2008. By this point, with developed countries' emissions essentially at a plateau, the major factor controlling the annual dynamics of global HFC-23 emissions became the historical rise of developing countries' HCFC-22 dispersive use production, which peaked in 2007. Thereafter in 2007-2009, incineration through CDM projects became a larger factor, reducing global HFC-23 emissions despite rapidly rising HCFC-22 feedstock production in developing countries.

Rigby, M, Muhle J, Miller BR, Prinn RG, Krummel PB, Steele LP, Fraser PJ, Salameh PK, Harth CM, Weiss RF, Greally BR, O'Doherty S, Simmonds PG, Vollmer MK, Reimann S, Kim J, Kim KR, Wang HJ, Olivier JGJ, Dlugokencky EJ, Dutton GS, Hall BD, Elkins JW.  2010.  History of atmospheric SF6 from 1973 to 2008. Atmospheric Chemistry and Physics. 10:10305-10320.   10.5194/acp-10-10305-2010   AbstractWebsite

We present atmospheric sulfur hexafluoride (SF(6)) mole fractions and emissions estimates from the 1970s to 2008. Measurements were made of archived air samples starting from 1973 in the Northern Hemisphere and from 1978 in the Southern Hemisphere, using the Advanced Global Atmospheric Gases Experiment (AGAGE) gas chromatographic-mass spectrometric (GC-MS) systems. These measurements were combined with modern high-frequency GC-MS and GC-electron capture detection (ECD) data from AGAGE monitoring sites, to produce a unique 35-year atmospheric record of this potent greenhouse gas. Atmospheric mole fractions were found to have increased by more than an order of magnitude between 1973 and 2008. The 2008 growth rate was the highest recorded, at 0.29 +/- 0.02 pmol mol(-1) yr(-1). A three-dimensional chemical transport model and a minimum variance Bayesian inverse method was used to estimate annual emission rates using the measurements, with a priori estimates from the Emissions Database for Global Atmospheric Research (EDGAR, version 4). Consistent with the mole fraction growth rate maximum, global emissions during 2008 were also the highest in the 1973-2008 period, reaching 7.4 +/- 0.6 Gg yr(-1) (1-sigma uncertainties) and surpassing the previous maximum in 1995. The 2008 values follow an increase in emissions of 48 +/- 20% since 2001. A second global inversion which also incorporated National Oceanic and Atmospheric Administration (NOAA) flask measurements and in situ monitoring site data agreed well with the emissions derived using AGAGE measurements alone. By estimating continent-scale emissions using all available AGAGE and NOAA surface measurements covering the period 2004-2008, with no pollution filtering, we find that it is likely that much of the global emissions rise during this five-year period originated primarily from Asian developing countries that do not report detailed, annual emissions to the United Nations Framework Convention on Climate Change (UNFCCC). We also find it likely that SF(6) emissions reported to the UNFCCC were underestimated between at least 2004 and 2005.

Muhle, J, Ganesan AL, Miller BR, Salameh PK, Harth CM, Greally BR, Rigby M, Porter LW, Steele LP, Trudinger CM, Krummel PB, O'Doherty S, Fraser PJ, Simmonds PG, Prinn RG, Weiss RF.  2010.  Perfluorocarbons in the global atmosphere: tetrafluoromethane, hexafluoroethane, and octafluoropropane. Atmospheric Chemistry and Physics. 10:5145-5164.   10.5194/acp-10-5145-2010   AbstractWebsite

We present atmospheric baseline growth rates from the 1970s to the present for the long-lived, strongly infrared-absorbing perfluorocarbons (PFCs) tetrafluoromethane (CF(4)), hexafluoroethane (C(2)F(6)), and octafluoropropane (C(3)F(8)) in both hemispheres, measured with improved accuracies (similar to 1-2%) and precisions (<0.3%, or <0.2 ppt (parts per trillion dry air mole fraction), for CF(4); <1.5%, or <0.06 ppt, for C(2)F(6); <4.5%, or <0.02 ppt, for C3F8) within the Advanced Global Atmospheric Gases Experiment (AGAGE). Pre-industrial background values of 34.7 +/- 0.2 ppt CF(4) and 0.1 +/- 0.02 ppt C(2)F(6) were measured in air extracted from Greenland ice and Antarctic firn. Anthropogenic sources are thought to be primary aluminum production (CF(4), C(2)F(6), C(3)F(8)), semiconductor production (C(2)F(6), CF(4), C(3)F(8)) and refrigeration use (C(3)F(8)). Global emissions calculated with the AGAGE 2-D 12-box model are significantly higher than most previous emission estimates. The sum of CF(4) and C(2)F(6) emissions estimated from aluminum production and non-metal production are lower than observed global top-down emissions, with gaps of similar to 6 Gg/yr CF(4) in recent years. The significant discrepancies between previous CF(4), C(2)F(6), and C(3)F(8) emission estimates and observed global top-down emissions estimated from AGAGE measurements emphasize the need for more accurate, transparent, and complete emission reporting, and for verification with atmospheric measurements to assess the emission sources of these long-lived and potent greenhouse gases, which alter the radiative budget of the atmosphere, essentially permanently, once emitted.

Muhle, J, Huang J, Weiss RF, Prinn RG, Miller BR, Salameh PK, Harth CM, Fraser PJ, Porter LW, Greally BR, O'Doherty S, Simmonds PG.  2009.  Sulfuryl fluoride in the global atmosphere. Journal of Geophysical Research-Atmospheres. 114   10.1029/2008jd011162   AbstractWebsite

The first calibrated high-frequency, high-precision, in situ atmospheric and archived air measurements of the fumigant sulfuryl fluoride (SO(2)F(2)) have been made as part of the Advanced Global Atmospheric Gas Experiment (AGAGE) program. The global tropospheric background concentration of SO(2)F(2) has increased by 5 +/- 1% per year from similar to 0.3 ppt (parts per trillion, dry air mol fraction) in 1978 to similar to 1.35 ppt in May 2007 in the Southern Hemisphere, and from similar to 1.08 ppt in 1999 to similar to 1.53 ppt in May 2007 in the Northern Hemisphere. The SO(2)F(2) interhemispheric concentration ratio was 1.13 +/- 0.02 from 1999 to 2007. Two-dimensional 12-box model inversions yield global total and global oceanic uptake atmospheric lifetimes of 36 +/- 11 and 40 +/- 13 years, respectively, with hydrolysis in the ocean being the dominant sink, in good agreement with 35 +/- 14 years from a simple oceanic uptake calculation using transfer velocity and solubility. Modeled SO2F2 emissions rose from similar to 0.6 Gg/a in 1978 to similar to 1.9 Gg/a in 2007, but estimated industrial production exceeds these modeled emissions by an average of similar to 50%. This discrepancy cannot be explained with a hypothetical land sink in the model, suggesting that only similar to 2/3 of the manufactured SO(2)F(2) is actually emitted into the atmosphere and that similar to 1/3 may be destroyed during fumigation. With mean SO(2)F(2) tropospheric mixing ratios of similar to 1.4 ppt, its radiative forcing is small and it is probably an insignificant sulfur source to the stratosphere. However, with a high global warming potential similar to CFC-11, and likely increases in its future use, continued atmospheric monitoring of SO(2)F(2) is warranted.

Rhew, RC, Miller BR, Weiss RF.  2008.  Chloroform, carbon tetrachloride and methyl chloroform fluxes in southern California ecosystems. Atmospheric Environment. 42:7135-7140.   10.1016/j.atmosenv.2008.05.038   AbstractWebsite

Chloroform (CHCl3), carbon tetrachloride (CCl4), and methyl chloroform (CH3CCl3) are important carriers of chlorine to the stratosphere and account for an estimated 159 of the total organic chlorine in the troposphere, roughly equivalent to chlorine load due to methyl chloride (CH3Cl). The tropospheric burden of chlorine has declined since 1994, largely due to the restriction of CH3CCl3 and CCl4 use as specified by the Montreal Protocol. However, few field studies have been conducted on the terrestrial-atmosphere exchange of these chlorinated hydrocarbons, leading to uncertainties about the natural cycling of these trace gases. This work shows the results of 75 flux measurements conducted in a variety of southern California ecosystems, including coast sagebrush, chamise chaparral, creosote bush scrub, shoreline, and coastal salt marsh. We find no evidence of a significant soil sink in these ecosystems but rather a small net source of CHCl3 and possibly CCl4. (c) 2008 Elsevier Ltd. All rights reserved.

Miller, BR, Weiss RF, Salameh PK, Tanhua T, Greally BR, Muhle J, Simmonds PG.  2008.  Medusa: A sample preconcentration and GC/MS detector system for in situ measurements of atmospheric trace halocarbons, hydrocarbons, and sulfur compounds. Analytical Chemistry. 80:1536-1545.   10.1021/ac702084k   AbstractWebsite

Significant changes have occurred in the anthropogenic emissions of many compounds related to the Kyoto and Montreal Protocols within the past 20 years and many of their atmospheric abundances have responded dramatically. Additionally, there are a number of related natural compounds with underdetermined source or sink budgets. A new instrument, Medusa, was developed to make the high frequency in situ measurements required for the determination of the atmospheric lifetimes and emissions of these compounds. This automated system measures a wide range of halocarbons, hydrocarbons, and sulfur compounds involved in ozone depletion and/or climate forcing, from the very volatile perfluorocarbons (PFCs, e.g., CF(4) and CF(3)CF(3)) and hydrofluorocarbons (HFCs, e.g., CH(3)CF(3)) to the higher-boiling point solvents (such as CH(3)CCl(3) and CCl(2)= CCl(2)) and CHBr(3). A network of Medusa systems worldwide provides 12 in situ ambient air measurements per day of more than 38 compounds of part per trillion mole fractions and precisions up to 0.1% RSD at the five remote field stations operated by the Advanced Global Atmospheric Gases Experiment (AGAGE). Ihis custom system couples gas chromatography/mass spectrometry (GC/MSD) with a novel scheme for cryogen-free low-temperature preconcentration (-165 degrees C) of analytes from 2 L samples in a two-trap process using HayeSep D adsorbent.

Deeds, DA, Muhle J, Weiss RF.  2008.  Tetrafluoromethane in the deep North Pacific Ocean. Geophysical Research Letters. 35   10.1029/2008gl034355   AbstractWebsite

Dissolved tetrafluoromethane (CF(4)) has been measured for the first time in the North Pacific Ocean. Surface water collected during calm weather is near equilibrium with the modern atmosphere. Deep water, isolated from atmospheric exchange for centuries, is near equilibrium with the preindustrial atmosphere, after accounting for an expected 5% addition of this low-solubility gas due to air injection during high-latitude deep-water formation. These results strongly suggest that dissolved CF(4) is conservative in seawater and that the oceanic imprint of anthropogenic increases in atmospheric CF(4) can be used as a time-dependent tracer of ocean ventilation and subsurface circulation processes. Although the continental lithosphere is a source of natural atmospheric CF(4), we find no evidence of an oceanic lithospheric CF(4) input into deep Pacific waters. The estimated upper limit of a potential oceanic lithospheric CF(4) flux to the global atmosphere is on the order of 4% of that from the continental lithosphere.

Deeds, DA, Vollmer MK, Kulongoski JT, Miller BR, Muhle J, Harth CM, Izbicki JA, Hilton DR, Weiss RF.  2008.  Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters. Geochimica Et Cosmochimica Acta. 72:999-1013.   10.1016/j.gca.2007.11.027   AbstractWebsite

Dissolved tetrafluoromethane (CF(4)) and sulfur hexafluoride (SF(6)) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF(4) and SF(6) are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF(4) from the lithosphere. A gradual basin-wide enhancement in dissolved CF(4) and SF(6) concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF(4) and SF(6) concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF(4), but not of SF(6), is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF(4) and SF(6) into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF(4) and SF(6). (c) 2007 Elsevier Ltd. All rights reserved.

Nevison, CD, Mahowald NM, Weiss RF, Prinn RG.  2007.  Interannual and seasonal variability in atmospheric N2O. Global Biogeochemical Cycles. 21   10.1029/2006gb002755   AbstractWebsite

The increase in atmospheric N2O observed over the last century reflects large- scale human perturbations to the global nitrogen cycle. High- precision measurements of atmospheric N2O over the last decade reveal subtle signals of interannual variability (IAV) superimposed upon the more prominent growth trend. Anthropogenic sources drive the underlying growth in N2O, but are probably too monotonic to explain most of the observed IAV. The causes of both seasonal and interannual variability in atmospheric N2O are explored on the basis of comparisons of a 1993 - 2004 atmospheric transport simulation to observations of N2O at five stations of the Advanced Global Atmospheric Gases Experiment (AGAGE). The complementary tracers chlorofluorocarbons (CFCs) 11 and 12 and SF6 also are examined. The model simulation does not include a stratospheric sink and thus isolates the effects of surface sources and tropospheric transport. Both model and observations yield correlations in seasonal and interannual variability among species, but only in a few cases are model and observed variability correlated to each other. The results suggest that tropospheric transport contributes substantially to observed variability, especially at Samoa station. However, some features of observed variability are not explained by the model simulation and appear more consistent with a stratospheric influence. At Mace Head, Ireland, N2O and CFC growth rate anomalies are weakly correlated to IAV in polar winter lower stratospheric temperature, a proxy for the strength of the mean meridional stratospheric circulation. Seasonal and interannual variability in the natural sources of N2O may also contribute to observed variability in atmospheric N2O.

Simmonds, PG, Derwent RG, Manning AJ, Fraser PJ, Krummel PB, O'Doherty S, Prinn RG, Cunnold DM, Miller BR, Wang HJ, Ryall DB, Porter LW, Weiss RF, Salameh PK.  2004.  AGAGE observations of methyl bromide and methyl chloride at Mace Head, Ireland, and Cape Grim, Tasmania, 1998-2001. Journal of Atmospheric Chemistry. 47:243-269.   10.1023/B:JOCH.0000021136.52340.9c   AbstractWebsite

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 a strong 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).

Min, DH, Bullister JL, Weiss RF.  2002.  Anomalous chlorofluorocarbons in the Southern California Borderland Basins. Geophysical Research Letters. 29   10.1029/2002gl015408   AbstractWebsite

During the past two decades, unexpectedly high concentrations of chlorofluorocarbons (CFCs) have been observed in the bottom waters of the Southern California Borderland Basins (SCBB), with relatively constant spatial distribution patterns. In contrast to offshore waters in this region, CFC concentrations below the oxygen minimum layer (OML) in the deep SCBB increase with depth. The uniformity of the bottom-enhanced CFC signals and the near-zero levels of tritium suggest that this feature is likely maintained by release of CFCs from sediments and vertical mixing, and not by dumped CFC-bearing materials or an intrusion of recently ventilated waters. We hypothesize that CFC scavenging processes, either on particulate organic matter or hydrocarbon residues from the adjacent natural seeps, occur in these high-productivity near-surface coastal waters. The subsequent release of CFCs at the bottom boundary layer during the degradation of particulate material may cause the anomalous CFC distributions in the SCBB.

O'Doherty, S, Simmonds PG, Cunnold DM, Wang HJ, Sturrock GA, Fraser PJ, Ryall D, Derwent RG, Weiss RF, Salameh P, Miller BR, Prinn RG.  2001.  In situ chloroform measurements at Advanced Global Atmospheric Gases Experiment atmospheric research stations from 1994 to 1998. Journal of Geophysical Research-Atmospheres. 106:20429-20444.   10.1029/2000jd900792   AbstractWebsite

Measurements of atmospheric chloroform (CHCl3) by in situ gas chromatography using electron capture detection are reported from the Advanced Global Atmospheric Gases Experiment (AGAGE) network of atmospheric research stations. They are some of the most comprehensive in situ, high-frequency measurements to be reported for CHCl3 and provide valuable information not only on clean "baseline" mixing ratios but also on local and regional sources. Emissions from these sources cause substantial periodic increases in CHCl3 concentrations above their baseline levels, which can be used to identify source strengths. This is particularly the case for measurements made at Mace Head, Ireland. Furthermore, these local sources of CHCl3 emissions are significant in relation to current estimates of global emissions and illustrate that the understanding of competing sources and sinks of CHCl3 is still fragmentary. These observations also show that CHCl3 has a very pronounced seasonal cycle with a summer minimum and winter maximum presumably resulting from enhanced destruction by OH in the summer. The amplitude of the cycle is dependent on sampling location. Over the 57 months of in situ measurements a global average baseline concentration of 8.9 +/-0.1 ppt was determined with no appreciable trend in the baseline detected.

Alexander, B, Vollmer MK, Jackson T, Weiss RF, Thiemens MH.  2001.  Stratospheric CO2 isotopic anomalies and SF6 and CFC tracer concentrations in the Arctic polar vortex. Geophysical Research Letters. 28:4103-4106.   10.1029/2001gl013692   AbstractWebsite

Isotopic measurements (delta O-17 and delta O-18) Of CO2 along with concentration measurements of SF6, CC1(3)F (CFC-11), CC1(2)F(2) (CFC-12) and CC1(2)FCC1F(2) (CFC-113) in stratospheric samples collected within the Arctic polar vortex are reported. These are the first simultaneous measurements of the concentration of fluorinated compounds and the complete oxygen isotopic composition Of CO2 in the middle atmosphere. A mass-independent anomaly in the oxygen isotopic composition Of CO2 is observed that arises from isotopic exchange with stratospheric O(D-1) derived from O-3 photolysis. The data exhibit a strong anti-correlation between the Delta O-17 (the degree of the mass-independent anomaly) and molecular tracer concentrations. The potential ability of tl-ris isotopic proxy to trace mesospheric and stratospheric transport is discussed.

Prinn, RG, Huang J, Weiss RF, Cunnold DM, Fraser PJ, Simmonds PG, McCulloch A, Harth C, Salameh P, O'Doherty S, Wang RHJ, Porter L, Miller BR.  2001.  Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades. Science. 292:1882-1888.   10.1126/science.1058673   AbstractWebsite

The hydroxyl radical (OH) is the dominant oxidizing chemical in the atmosphere. It destroys most air pollutants and many gases involved in ozone depletion and the greenhouse effect. Global measurements of 1,1,1-trichloroethane (CH3CCl3, methyl chloroform) provide an accurate method for determining the global and hemispheric behavior of OH. Measurements show that CH3CCl3 Levels rose steadily from 1978 to reach a maximum in 1992 and then decreased rapidly to levels in 2000 that were Lower than the levels when measurements began in 1978. Analysis of these observations shows that global OH Levels were growing between 1978 and 1988, but the growth rate was decreasing at a rate of 0.23 +/- 0.18% year(-2), so that OH Levels began declining after 1988. Overall, the global average OH trend between 1978 and 2000 was -0.64 +/- 0.60% year(-1). These variations imply important and unexpected gaps in current understanding of the capability of the atmosphere to cleanse itself.

Miller, BR, Huang J, Weiss RF, Prinn RG, Fraser PJ.  1998.  Atmospheric trend and lifetime of chlorodifluoromethane (HCFC-22) and the global tropospheric OH concentration. Journal of Geophysical Research-Atmospheres. 103:13237-13248.   10.1029/98jd00771   AbstractWebsite

Concentrations of CHClF2 (HCFC-22) in clean background air collected at Cape Grim, Tasmania, over the period 1978-1996, and at La Jolla, California, over the period 1992-1997, have been measured by oxygen-doped electron capture detection gas chromatography. The mid-1996 dry-air mole fractions and trends were 116.7 parts per trillion (ppt) and 6.0 ppt yr(-1) in Cape Grim and 132.4 ppt and 5.5 ppt yr(-1) in California: respectively. These observations, together with estimates of industrial emissions, have been fitted to a two-dimensional global atmospheric model by an optimal estimation inversion technique to yield estimated tropospheric and total atmospheric Lifetimes for chemical destruction of CHClF2 of 9.1(-2.8)(+4.4) years and 10.0(-3.0)(+4.4) years, respectively. These lifetimes Correspond to a temperature- and density-weighed global tropospheric OH abundance of 11.0(-3.6)(+5.0) x 10(5) radical cm(-3), which is in statistical agreement with our recent more accurate estimate of OH abundance based on measurements of CH3CCl3. Our analysis suggests that, compared to current industrial estimates, southern hemisphere emissions are higher, global emissions are larger in earlier years and smaller in later years, and, finally, production by nonreporting companies is less.

Fraser, P, Cunnold D, Alyea F, Weiss R, Prinn R, Simmonds P, Miller B, Langenfelds R.  1996.  Lifetime and emission estimates of 1,1,2-trichlorotrifluorethane (CFC-113) from daily global background observations June 1982 June 1994. Journal of Geophysical Research-Atmospheres. 101:12585-12599.   10.1029/96jd00574   AbstractWebsite

Observations every two hours of CCl2FCClF2 at Mace Head, Ireland (February 1987-June 1994); Cape Meares, Oregon (April 1984-June 1989); Ragged Point, Barbados (October 1985-June 1994); Cape Matatula, Samoa (October 1985-June 1989 and January 1992-June 1994); and Cape Grim, Tasmania (June 1982-June 1994) are reported, The observations from Cape Grim have been extended back to 1978 using archived air samples. The global atmospheric abundance of CCl2FCClF2 is indicated to have been growing exponentially between 1978 and 1987 with an e-folding time of approximately 7.6 years; it has been growing less rapidly since that time. On January 1, 1994, the mean inferred northern hemispheric mixing ratio in the lower troposphere was 84.4 +/- 0.4 ppt and the southern hemispheric value was 80.6 +/- 0.4 ppt; the global growth rate in 1991-1993 is estimated to have averaged approximately 3.1 +/- 0.1 ppt/year. The differences between the northern and southern hemispheric concentrations are calculated to be consistent with the almost entirely northern hemispheric release of this gas. The annual release estimates of CCl2FCClF2 by industry, which include estimates of eastern European emissions, fairly consistently exceed those deduced from the measurements by approximately 10% from 1980 to 1993. The uncertainties in each estimate is approximately 5%. This difference suggests that up to 10% of past production might not yet have been released. The measurements indicate that atmospheric releases of CCl2FCClF2 have been decreasing rapidly since 1989 and in 1993 amounted to 78 +/- 27 x 10(6) kg or 42 +/- 15% of the 1985-1987 emissions.

Cunnold, DM, Fraser PJ, Weiss RF, Prinn RG, Simmonds PG, Miller BR, Alyea FN, Crawford AJ.  1994.  Global trends and annual releases of CCl3F and CCl2F2 estimated from ALE/GAGE and other measurements from July 1978 to June 1991. Journal of Geophysical Research-Atmospheres. 99:1107-1126.   10.1029/93jd02715   AbstractWebsite

Thirteen years of Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment CCl3F and CCl2F2 measurements at five remote, surface, globally distributed sites are analyzed. Comparisons are made against shipboard measurements by the Scripps Institution of Oceanography group and archived air samples collected at Cape Grim, Tasmania, since 1978. CCl3F in the lower troposphere was increasing at an average rate of 9.2 ppt/yr over the period July 1978 to June 1988. CCl2F2 was increasing at an average 17.3 ppt/yr in the lower troposphere over the same period. However, between July 1988 and June 1991 the increases of CCl3F and CCl2F2 in this region have averaged just 7.0 ppt/yr and 15.7 ppt/yr, respectively. The rate of increase has been decreasing 2.4 ppt/yr and 2.9 ppt/yr(2) over this 3-year period. Based on a recent scenario of the global releases of these compounds and using the new calibration scale SIO 1993, the equilibrium lifetimes are estimated to be 44(-10)(+17) and 180(_81)(+820) years for CCl3F and CCl2F2, respectively. Using these lifetime estimates and a two-dimensional model, it is estimated that global releases of these two chlorofluorocarbons in 1990 were 249+/-28 x 10(6) kg for CCl3F and 366+/-30 x 10(6) kg for CCl2F2. It is also estimated that combined releases of these chlorofluorocarbons in 1990 were 21+/-5% less than those in 1986.