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Book Chapter
Forster, P, Ramaswamy V, Artaxo P, Berntsen J, Betts R, Fahey DW, Haywood J, Lean J, Lowe DC, Myhre G, Nganga J, Prinn R, Raga G, Schulz M, van Dorland R, Bodeker G, Boucher O, Collins WD, Conway TJ, Dlugokencky E, Elkins JW, Etheridge D, Foukal P, Fraser P, Geller M, Joos F, Keeling CD, Keeling R, Kinne S, Lassey K, Lohmann U, Manning AC, Montzka SA, Oram D, O'Shaughnessy K, Piper SC, Plattner GK, Ponater M, Ramankutty N, Reid GC, Rind D, Rosenlof KH, Sausen R, Schwarzkopf D, Solanki SK, Stenchikov G, Stuber N, Takemura T, Textor C, Wang R, Weiss R, Whorf T.  2007.  Changes in atmospheric constituents and in radiative forcing. Climate Change 2007 : The Physical Science Basis : Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change. ( Solomon S, Qin D, Manning M, Chen Z, Marquis M, Averyt K, Tignor M, Miller H, Eds.).:129-234., Cambridge; New York: Cambridge University Press Abstract

For policymakers -- Technical summary -- Historical overview of climate change science -- Changes in atmospheric constituents and radiative forcing -- Observations: atmospheric surface and climate change -- Observations: changes in snow, ice, and frozen ground -- Observations: ocean climate change and sea level -- Paleoclimate -- Coupling between changes in the climate system and biogeochemistry -- Climate models and their evaluation -- Understanding and attributing climate change -- Global climate projections -- Regional climate projections -- Annex I: Glossary -- Annex II: Contributors to the IPCC WGI Fourth Assessment Report -- Annex III: Reviewers of the IPCC WGI Fourth Assessment Report -- Annex IV: Acronyms.

Montzka, SA, Fraser PJ, Butler JH, Connell PS, Cunnold DM, Daniel JS, Derwent RG, Lal S, McCulloch A, Oram D, Reeves CE, Sanhueza E, Steele LP, Velders GJM, Weiss RF, Zander R.  2003.  Controlled substances and other source gases. Scientific assessment of ozone depletion, 2002 (World Meteorological Organization, Global Ozone Research and Monitoring Project, Report 47). :83., Washington, DC: National Oceanic and Atmospheric Administration Abstract
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Weiss, RF.  1969.  Dissolved argon, nitrogen and total carbonate in the Red Sea brines. Hot brines and recent heavy metal deposits in the Red Sea; a geochemical and geophysical account. ( Degens ET, Ross DA, Eds.).:254-260., New York: Springer-Verlag Abstract
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Clerbaux, C, Cunnold DM, Anderson J, Engel AEJ, Fraser PJ, Mahieu E, Manning A, Miller J, Montzka SA, Nassar R, Prinn R, Reimann S, Rinsland CP, Simmonds P, Verdonik D, Weiss R, Wuebbles D, Yokouchi K.  2007.  Long-lived compounds. Scientific assessment of ozone depletion, 2006 (World Meteorological Organization, Global Ozone Research and Monitoring Project, Report 50). :83., Geneva, Switzerland: World Meteorological Organization Abstract
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Prinn, RG, Zander R, Cunnold DM, Elkins JW, Engel A, Fraser PJ, Gunson MR, Ko MKW, Mahieu E, Midgley PM, Russel III JM, Volk CM, Weiss RF.  1999.  Long-lived ozone-related compounds. Scientific assessment of ozone depletion, 1998 (World Meteorological Organization, Global Ozone Research and Monitoring Project Report 44). :54., Washington, DC: National Oceanic and Atmospheric Administration Abstract
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Penkett, SA, Butler JH, Kurylo MJ, Reeves CE, Rodriguez JM, Singh H, Toohey D, Weiss R.  1995.  Methyl bromide. Scientific assessment of ozone depletion: 1994 (World Meterological Organization, Global Ozone Research and Monitoring Report). ( World Meteorological O, Ed.).:26., Geneva, Switzerland; Nairobi, Kenya; Washington, DC, USA: World Meteorological Organization Abstract
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Kurylo, MJ, Rodriguez JM, Andreae MO, Atlas EL, Blake DR, Butler JH, Lal S, Lary DJ, Midgley PM, Montzka SA, Novelli PC, Reeves CE, Simmonds PG, Steele LP, Sturges WT, Weiss RF, Yokouchi Y.  1999.  Short-lived ozone-related compounds. Scientific assessment of ozone depletion, 1998 (World Meteorological Organization, Global Ozone Research and Monitoring Project Report 44). :56., Washington, DC: National Oceanic and Atmospheric Administration Abstract
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Conference Proceedings
Weiss, RF, Kirsten OH, Ackermann R, Ramo S.  1977.  Free vehicle instrumentation for the in-situ measurement of processes controlling the formation of deep-sea ferromanganese nodules. OCEANS '77 Conference Record. , New York, N.Y., United States (USA): Inst. Electric. and Electron. Eng., New York, N.Y.   10.1109/OCEANS.1977.1154352   Abstract

This paper describes the free vehicle instrumentation under development for the Manganese Nodule Program (MANOP) of the International Decade for Ocean Exploration (IDOE). Principal emphasis is being placed on the MANOP Bottom Lander, a device designed to carry out in situ chemical flux experiments at the seawater-sediment interface at depths up to 6 km. This device will collect time-series water samples from three separate bottom chamber experiments, each of which can be spiked with various chemical and radioisotopic tracers. The device will also make oxygen and pH measurements in each chamber and will take box core samples under each chamber before returning to the surface. All operations will be microprocessor-controlled with data storage capability and with an acoustic data-link to the surface. Deployments will be for periods of up to 1 year.

Journal Article
Petrenko, VV, Smith AM, Brook EJ, Lowe D, Riedel K, Brailsford G, Hua Q, Schaefer H, Reeh N, Weiss RF, Etheridge D, Severinghaus JP.  2009.  14CH4 measurements in Greenland ice: investigating last glacial termination CH4 sources. Science. 324:506-508.   10.1126/science.1168909   AbstractWebsite

The cause of a large increase of atmospheric methane concentration during the Younger Dryas-Preboreal abrupt climatic transition (similar to 11,600 years ago) has been the subject of much debate. The carbon-14 (C-14) content of methane ((CH4)-C-14) should distinguish between wetland and clathrate contributions to this increase. We present measurements of (CH4)-C-14 in glacial ice, targeting this transition, performed by using ice samples obtained from an ablation site in west Greenland. Measured (CH4)-C-14 values were higher than predicted under any scenario. Sample (CH4)-C-14 appears to be elevated by direct cosmogenic C-14 production in ice. C-14 of CO was measured to better understand this process and correct the sample (CH4)-C-14. Corrected results suggest that wetland sources were likely responsible for the majority of the Younger Dryas-Preboreal CH4 rise.

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).

Zhang, G, Yao B, Vollmer MK, Montzka SA, Mühle J, Weiss RF, O'Doherty S, Li Y, Fang S, Reimann S.  2017.  Ambient mixing ratios of atmospheric halogenated compounds at five background stations in China. Atmospheric Environment. 160:55-69.   10.1016/j.atmosenv.2017.04.017   AbstractWebsite

High precision measurements of three chlorofluorocarbons (CFCs), three hydrochlorofluorocarbons (HCFCs), six hydrofluorocarbons (HFCs), three perfluorocarbons (PFCs), and sulfur hexafluoride (SF6) were made at five Chinese background stations from January 2011 to December 2012. Their station means in the background air were 239.5 ± 0.69 parts-per-trillion dry-air mole fraction mixing ratios (ppt) for CFC-11, 536.5 ± 1.49 ppt for CFC-12, 74.66 ± 0.09 ppt for CFC-113, 232.1 ± 4.77 ppt for HCFC-22, 23.78 ± 0.29 ppt for HCFC-141b, 22.92 ± 0.42 ppt for HCFC-142b, 11.75 ± 0.43 ppt for HFC-125, 71.32 ± 1.35 ppt for HFC-134a, 13.62 ± 0.43 ppt for HFC-143a, 9.10 ± 1.26 ppt for HFC-152a, 25.45 ± 0.1 ppt for HFC-23, 7.28 ± 0.48 ppt for HFC-32, 4.32 ± 0.03 ppt for PFC-116, 0.63 ± 0.04 ppt for PFC-218, 1.36 ± 0.01 ppt for PFC-318, and 7.67 ± 0.03 ppt for SF6, respectively, which were comparable with those measured at the two Northern Hemisphere (NH) AGAGE stations: Mace Head, Ireland (MHD) and Trinidad Head, California, USA (THD). Compared with our results for earlier years from in-situ measurement at SDZ, background-air mixing ratios of CFCs are now declining, while those for HCFCs, HFCs, PFCs, and SF6 are still increasing. The ratios of the number of sampling events in which measured mixing ratios were elevated above background (pollution events) relative to the total sample frequency (POL/SUM) for CFCs, HCFCs, and HFCs were found to be station dependent, generally LAN > SDZ > LFS > XGL > WLG. The enhancement (△, polluted mixing ratios minus background mixing ratios) generally show distinct patterns, with HCFCs (40.7–175.4 ppt) > HFCs (15.8–66.3 ppt)> CFCs (15.8–33.8 ppt)> PFCs (0.1–0.9 ppt) at five stations, especially for HCFC-22 ranging from 36.9 ppt to 138.2 ppt. Combining with the molecular weights, our findings imply biggest emissions of HCFCs in the regions around these Chinese sites compared to HFCs and CFCs, while the smallest of PFCs, consistent with CFCs being phased out and replaced with HCFCs in China. In addition, relative emission strengths (emission was expressed by mole fractions) of these halocarbons in China were inferred as HCFC-22 > HCFC-141b > HFC-134a > HCFC-142b for the Yangtze River Delta (YRD) and as HCFC-22 > HCFC-142b > HCFC-141b ≈ HFC-134a in the North China Plain (NCP).

Stohl, A, Seibert P, Arduini J, Eckhardt S, Fraser P, Greally BR, Lunder C, Maione M, Muhle J, O'Doherty S, Prinn RG, Reimann S, Saito T, Schmidbauer N, Simmonds PG, Vollmer MK, Weiss RF, Yokouchi Y.  2009.  An analytical inversion method for determining regional and global emissions of greenhouse gases: Sensitivity studies and application to halocarbons. Atmospheric Chemistry and Physics. 9:1597-1620.   10.5194/acp-9-1597-2009   AbstractWebsite

A new analytical inversion method has been developed to determine the regional and global emissions of long-lived atmospheric trace gases. It exploits in situ measurement data from three global networks and builds on backward simulations with a Lagrangian particle dispersion model. The emission information is extracted from the observed concentration increases over a baseline that is itself objectively determined by the inversion algorithm. The method was applied to two hydrofluorocarbons (HFC-134a, HFC-152a) and a hydrochlorofluorocarbon (HCFC-22) for the period January 2005 until March 2007. Detailed sensitivity studies with synthetic as well as with real measurement data were done to quantify the influence on the results of the a priori emissions and their uncertainties as well as of the observation and model errors. It was found that the global a posteriori emissions of HFC-134a, HFC-152a and HCFC-22 all increased from 2005 to 2006. Large increases (21%, 16%, 18%, respectively) from 2005 to 2006 were found for China, whereas the emission changes in North America (-9%, 23%, 17%, respectively) and Europe (11%, 11%,-4%, respectively) were mostly smaller and less systematic. For Europe, the a posteriori emissions of HFC-134a and HFC-152a were slightly higher than the a priori emissions reported to the United Nations Framework Convention on Climate Change (UNFCCC). For HCFC-22, the a posteriori emissions for Europe were substantially (by almost a factor 2) higher than the a priori emissions used, which were based on HCFC consumption data reported to the United Nations Environment Programme (UNEP). Combined with the reported strongly decreasing HCFC consumption in Europe, this suggests a substantial time lag between the reported time of the HCFC-22 consumption and the actual time of the HCFC-22 emission. Conversely, in China where HCFC consumption is increasing rapidly according to the UNEP data, the a posteriori emissions are only about 40% of the a priori emissions. This reveals a substantial storage of HCFC-22 and potential for future emissions in China. Deficiencies in the geographical distribution of stations measuring halocarbons in relation to estimating regional emissions are also discussed in the paper. Applications of the inversion algorithm to other greenhouse gases such as methane, nitrous oxide or carbon dioxide are foreseen for the future.

Vollmer, MK, Young D, Trudinger CM, Muhle J, Henne S, Rigby M, Park S, Li S, Guillevic M, Mitrevski B, Harth CM, Miller BR, Reimann S, Yao B, Steele LP, Wyss SA, Lunder CR, Arduini J, McCulloch A, Wu S, Rhee TS, Wang RHJ, Salameh PK, Hermansen O, Hill M, Langenfelds RL, Ivy D, O'Doherty S, Krummel PB, Maione M, Etheridge DM, Zhou LX, Fraser PJ, Prinn RG, Weiss RF, Simmonds PG.  2018.  Atmospheric histories and emissions of chlorofluorocarbons CFC-13 (CClF3), Sigma CFC-114 (C2Cl2F4), and CFC-115 (C2ClF5). Atmospheric Chemistry and Physics. 18:979-1002.   10.5194/acp-18-979-2018   AbstractWebsite

Based on observations of the chlorofluorocarbons CFC-13 (chlorotrifluoromethane), Sigma CFC-114 (combined measurement of both isomers of dichlorotetrafluoroethane), and CFC-115 (chloropentafluoroethane) in atmospheric and firn samples, we reconstruct records of their tropospheric histories spanning nearly 8 decades. These compounds were measured in polar firn air samples, in ambient air archived in canisters, and in situ at the AGAGE (Advanced Global Atmospheric Gases Experiment) network and affiliated sites. Global emissions to the atmosphere are derived from these observations using an inversion based on a 12-box atmospheric transport model. For CFC-13, we provide the first comprehensive global analysis. This compound increased monotonically from its first appearance in the atmosphere in the late 1950s to a mean global abundance of 3.18 ppt (dry-air mole fraction in parts per trillion, pmol mol(-1)) in 2016. Its growth rate has decreased since the mid-1980s but has remained at a surprisingly high mean level of 0.02 ppt yr(-1) since 2000, resulting in a continuing growth of CFC-13 in the atmosphere. Sigma CFC-114 increased from its appearance in the 1950s to a maximum of 16.6 ppt in the early 2000s and has since slightly declined to 16.3 ppt in 2016. CFC-115 increased monotonically from its first appearance in the 1960s and reached a global mean mole fraction of 8.49 ppt in 2016. Growth rates of all three compounds over the past years are significantly larger than would be expected from zero emissions. Under the assumption of unchanging lifetimes and atmospheric transport patterns, we derive global emissions from our measurements, which have remained unexpectedly high in recent years: mean yearly emissions for the last decade (2007-2016) of CFC-13 are at 0.48 +/- 0.15 kt yr(-1) (> 15% of past peak emissions), of 6 CFC-114 at 1.90 +/- 0.84 kt yr(-1) (similar to 10% of peak emissions), and of CFC-115 at 0.80 +/- 0.50 kt yr(-1) (> 5% of peak emissions). Mean yearly emissions of CFC-115 for 2015-2016 are 1.14 +/- 0.50 kt yr(-1) and have doubled compared to the 2007-2010 minimum. We find CFC-13 emissions from aluminum smelters but if extrapolated to global emissions, they cannot account for the lingering global emissions determined from the atmospheric observations. We find impurities of CFC-115 in the refrigerant HFC-125 (CHF2CF3) but if extrapolated to global emissions, they can neither account for the lingering global CFC-115 emissions determined from the atmospheric observations nor for their recent increases. We also conduct regional inversions for the years 2012-2016 for the northeastern Asian area using observations from the Korean AGAGE site at Gosan and find significant emissions for Sigma CFC-114 and CFC-115, suggesting that a large fraction of their global emissions currently occur in northeastern Asia and more specifically on the Chinese mainland.

Vollmer, MK, Muhle J, Trudinger CM, Rigby M, Montzka SA, Harth CM, Miller BR, Henne S, Krummel PB, Hall BD, Young D, Kim J, Arduini J, Wenger A, Yao B, Reimann S, O'Doherty S, Maione M, Etheridge DM, Li SL, Verdonik DP, Park S, Dutton G, Steele LP, Lunder CR, Rhee TS, Hermansen O, Schmidbauer N, Wang RHJ, Hill M, Salameh PK, Langenfelds RL, Zhou LX, Blunier T, Schwander J, Elkins JW, Butler JH, Simmonds PG, Weiss RF, Prinn RG, Fraser PJ.  2016.  Atmospheric histories and global emissions of halons H-1211 (CBrClF2), H-1301 (CBrF3), and H-2402 (CBrF2CBrF2). Journal of Geophysical Research-Atmospheres. 121:3663-3686.   10.1002/2015jd024488   AbstractWebsite

We report ground-based atmospheric measurements and emission estimates for the halons H-1211 (CBrClF2), H-1301 (CBrF3), and H-2402 (CBrF2CBrF2) from the AGAGE (Advanced Global Atmospheric Gases Experiment) and the National Oceanic and Atmospheric Administration global networks. We also include results from archived air samples in canisters and from polar firn in both hemispheres, thereby deriving an atmospheric record of nearly nine decades (1930s to present). All three halons were absent from the atmosphere until approximate to 1970, when their atmospheric burdens started to increase rapidly. In recent years H-1211 and H-2402 mole fractions have been declining, but H-1301 has continued to grow. High-frequency observations show continuing emissions of H-1211 and H-1301 near most AGAGE sites. For H-2402 the only emissions detected were derived from the region surrounding the Sea of Japan/East Sea. Based on our observations, we derive global emissions using two different inversion approaches. Emissions for H-1211 declined from a peak of 11ktyr(-1) (late 1990s) to 3.9ktyr(-1) at the end of our record (mean of 2013-2015), for H-1301 from 5.4ktyr(-1) (late 1980s) to 1.6ktyr(-1), and for H-2402 from 1.8ktyr(-1) (late 1980s) to 0.38ktyr(-1). Yearly summed halon emissions have decreased substantially; nevertheless, since 2000 they have accounted for approximate to 30% of the emissions of all major anthropogenic ozone depletion substances, when weighted by ozone depletion potentials.

Vollmer, MK, Miller BR, Rigby M, Reimann S, Muhle J, Krummel PB, O'Doherty S, Kim J, Rhee TS, Weiss RF, Fraser PJ, Simmonds PG, Salameh PK, Harth CM, Wang RHJ, Steele LP, Young D, Lunder CR, Hermansen O, Ivy D, Arnold T, Schmidbauer N, Kim KR, Greally BR, Hill M, Leist M, Wenger A, Prinn RG.  2011.  Atmospheric histories and global emissions of the anthropogenic hydrofluorocarbons HFC-365mfc, HFC-245fa, HFC-227ea, and HFC-236fa. Journal of Geophysical Research-Atmospheres. 116   10.1029/2010jd015309   AbstractWebsite

We report on ground-based atmospheric measurements and emission estimates of the four anthropogenic hydrofluorocarbons (HFCs) HFC-365mfc (CH(3)CF(2)CH(2)CF(3), 1,1,1,3,3-pentafluorobutane), HFC-245fa (CHF(2)CH(2)CF(3), 1,1,1,3,3-pentafluoropropane), HFC-227ea (CF(3)CHFCF(3), 1,1,1,2,3,3,3-heptafluoropropane), and HFC-236fa (CF(3)CH(2)CF(3), 1,1,1,3,3,3-hexafluoropropane). In situ measurements are from the global monitoring sites of the Advanced Global Atmospheric Gases Experiment (AGAGE), the System for Observations of Halogenated Greenhouse Gases in Europe (SOGE), and Gosan (South Korea). We include the first halocarbon flask sample measurements from the Antarctic research stations King Sejong and Troll. We also present measurements of archived air samples from both hemispheres back to the 1970s. We use a two-dimensional atmospheric transport model to simulate global atmospheric abundances and to estimate global emissions. HFC-365mfc and HFC-245fa first appeared in the atmosphere only similar to 1 decade ago; they have grown rapidly to globally averaged dry air mole fractions of 0.53 ppt (in parts per trillion, 10(-12)) and 1.1 ppt, respectively, by the end of 2010. In contrast, HFC-227ea first appeared in the global atmosphere in the 1980s and has since grown to similar to 0.58 ppt. We report the first measurements of HFC-236fa in the atmosphere. This long-lived compound was present in the atmosphere at only 0.074 ppt in 2010. All four substances exhibit yearly growth rates of >8% yr(-1) at the end of 2010. We find rapidly increasing emissions for the foam-blowing compounds HFC-365mfc and HFC-245fa starting in similar to 2002. After peaking in 2006 (HFC-365mfc: 3.2 kt yr(-1), HFC-245fa: 6.5 kt yr(-1)), emissions began to decline. Our results for these two compounds suggest that recent estimates from long-term projections (to the late 21st century) have strongly overestimated emissions for the early years of the projections (similar to 2005-2010). Global HFC-227ea and HFC-236fa emissions have grown to average values of 2.4 kt yr(-1) and 0.18 kt y(r-)1 over the 2008-2010 period, respectively.

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.

Verhulst, KR, Karion A, Kim J, Salameh PK, Keeling RF, Newman S, Miller J, Sloop C, Pongetti T, Rao P, Wong C, Hopkins FM, Yadav V, Weiss RF, Duren RM, Miller CE.  2017.  Carbon dioxide and methane measurements from the Los Angeles Megacity Carbon Project - Part 1: calibration, urban enhancements, and uncertainty estimates. Atmospheric Chemistry and Physics. 17:8313-8341.   10.5194/acp-17-8313-2017   AbstractWebsite

We report continuous surface observations of carbon dioxide (CO2) and methane (CH4) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban-scale CO2 and CH4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four "extra-urban" sites including two "marine" sites located south of LA in La Jolla (LJO) and offshore on San Clemente Island (SCI), one "continental" site located in Victorville (VIC), in the high desert northeast of LA, and one "continental/mid-troposphere" site located on Mount Wilson (MWO) in the San Gabriel Mountains. We find that a local marine background can be established to within similar to 1 ppm CO2 and similar to 10 ppb CH4 using these local measurement sites. Overall, atmospheric carbon dioxide and methane levels are highly variable across Los Angeles. "Urban" and "suburban" sites show moderate to large CO2 and CH4 enhancements relative to a marine background estimate. The USC (University of Southern California) site near downtown LA exhibits median hourly enhancements of similar to 20 ppm CO2 and similar to 150 ppb CH4 during 2015 as well as similar to 15 ppm CO2 and similar to 80 ppb CH4 during mid-afternoon hours (12:00-16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is typically better than 0.1 ppm CO2 and 1 ppb CH4 based on the repeated standard gas measurements from the LA sites during the last 2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is due to the single-point calibration method; however, the uncertainty in the background mole fraction is much larger than the measurement uncertainty. The background uncertainty for the marine background estimate is similar to 10 and similar to 15% of the median mid-afternoon enhancement near downtown LA for CO2 and CH4, respectively. Overall, analytical and background uncertainties are small relative to the local CO2 and CH4 enhancements; however, our results suggest that reducing the uncertainty to less than 5% of the median mid-afternoon enhancement will require detailed assessment of the impact of meteorology on background conditions.

Bill, M, Rhew RC, Weiss RF, Goldstein AH.  2002.  Carbon isotope ratios of methyl bromide and methyl chloride emitted from a coastal salt marsh. Geophysical Research Letters. 29   10.1029/2001gl012946   AbstractWebsite

[1] Methyl bromide (CH3Br) and methyl chloride (CH3Cl) play important roles in stratospheric ozone depletion, but their atmospheric budgets have large uncertainties. The analysis of stable isotope composition of methyl halides may provide useful independent information for further constraining their budgets. Here we report the first measurements of CH3Br and CH3Cl stable carbon isotope ratios emitted from a biogenic source under in situ conditions. CH3Br and CH3Cl emissions from the salt marsh plant Batis maritima showed a strong diurnal variation in delta(13)C, from -65parts per thousand during the daytime to --12parts per thousand at night. The minimum delta(13)C values were observed at midday, coinciding with the time of greatest emissions and ambient temperature. At night, when the emissions were much smaller, the stable carbon isotopic ratios of CH3Br and CH3Cl became enriched in C-13. The daily mean delta(13)C of CH3Br and CH3Cl emissions, weighted by emission rate, were -43parts per thousand and -62parts per thousand respectively.

Rhoderick, G, Guenther F, Duewer D, Lee J, Kim JS, Hall B, Weiss R, Harth C, Reimann S, Vollmer M.  2014.  CCQM-P151 final report pilot study CCQM P151 halocarbons in dry whole air. Metrologia. 51 AbstractWebsite

The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a pilot study between National Metrology Institutes and atmospheric research laboratories for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2- trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2 tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels.

Simmonds, PG, Rigby M, McCulloch A, O'Doherty S, Young D, Mühle J, Krummel PB, Steele P, Fraser PJ, Manning AJ, Weiss RF, Salameh PK, Harth CM, Wang RHJ, Prinn RG.  2017.  Changing trends and emissions of hydrochlorofluorocarbons (HCFCs) and their hydrofluorocarbon (HFCs) replacements. Atmos. Chem. Phys.. 17:4641-4655.: Copernicus Publications   10.5194/acp-17-4641-2017   Abstract

High-frequency, in situ global observations of HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F), HCFC-142b (CH3CClF2) and HCFC-124 (CHClFCF3) and their main HFC replacements, HFC-134a (CH2FCF3), HFC-125 (CHF2CF3), HFC-143a (CH3CF3) and HFC-32 (CH2F2), have been used to determine their changing global growth rates and emissions in response to the Montreal Protocol and its recent amendments. Global mean mole fractions of HCFC-22, -141b, and -142b have increased throughout the observation period, reaching 234, 24.3 and 22.4 pmol mol−1, respectively, in 2015. HCFC-124 reached a maximum global mean mole fraction of 1.48 pmol mol−1 in 2007 and has since declined by 23 % to 1.14 pmol mol−1 in 2015. The HFCs all show increasing global mean mole fractions. In 2015 the global mean mole fractions (pmol mol−1) were 83.3 (HFC-134a), 18.4 (HFC-125), 17.7 (HFC-143a) and 10.5 (HFC-32).The 2007 adjustment to the Montreal Protocol required the accelerated phase-out of emissive uses of HCFCs with global production and consumption capped in 2013 to mitigate their environmental impact as both ozone-depleting substances and important greenhouse gases. We find that this change has coincided with a stabilisation, or moderate reduction, in global emissions of the four HCFCs with aggregated global emissions in 2015 of 449 ± 75 Gg yr−1, in CO2 equivalent units (CO2 eq.) 0.76 ± 0.1 Gt yr−1, compared with 483 ± 70 Gg yr−1 (0.82 ± 0.1 Gt yr−1 CO2 eq.) in 2010 (uncertainties are 1σ throughout this paper). About 79 % of the total HCFC atmospheric burden in 2015 is HCFC-22, where global emissions appear to have been relatively similar since 2011, in spite of the 2013 cap on emissive uses. We attribute this to a probable increase in production and consumption of HCFC-22 in Montreal Protocol Article 5 (developing) countries and the continuing release of HCFC-22 from the large banks which dominate HCFC global emissions. Conversely, the four HFCs all show increasing mole fraction growth rates with aggregated global HFC emissions of 327 ± 70 Gg yr−1 (0.65 ± 0.12 Gt yr−1 CO2 eq.) in 2015 compared to 240 ± 50 Gg yr−1 (0.47 ± 0.08 Gt yr−1 CO2 eq.) in 2010. We also note that emissions of HFC-125 and HFC-32 appear to have increased more rapidly averaged over the 5-year period 2011–2015, compared to 2006–2010. As noted by Lunt et al. (2015) this may reflect a change to refrigerant blends, such as R-410A, which contain HFC-32 and -125 as a 50 : 50 blend.

Ganesan, AL, Rigby M, Zammit-Mangion A, Manning AJ, Prinn RG, Fraser PJ, Harth CM, Kim KR, Krummel PB, Li S, Mühle J, O'Doherty SJ, Park S, Salameh PK, Steele LP, Weiss RF.  2014.  Characterization of uncertainties in atmospheric trace gas inversions using hierarchical Bayesian methods. Atmos. Chem. Phys.. 14:3855-3864.: Copernicus Publications   10.5194/acp-14-3855-2014   AbstractWebsite
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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.

Rhoderick, GC, Hall BD, Harth CM, Kim JS, Lee J, Montzka SA, Mühle J, Reimann S, Vollmer MK, Weiss RF.  2015.  Comparison of halocarbon measurements in an atmospheric dry whole air sample. Elem Sci Anth..   10.12952/journal.elementa.000075   Abstract

The growing awareness of climate change/global warming, and continuing concerns regarding stratospheric ozone depletion, will require continued measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track atmospheric mole fractions and assess the impact of policy on emission rates, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. Precise measurements of these species aid in determining small changes in their atmospheric abundance. A common source of standards/scales and/or well-documented agreement of different scales used to calibrate the measurement instrumentation are key to understanding many sets of data reported by researchers. This report describes the results of a comparison study among National Metrology Institutes and atmospheric research laboratories for the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC-12), trichlorofluoromethane (CFC-11), and 1,1,2-trichlorotrifluoroethane (CFC-113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC-22) and 1-chloro-1,1-difluoroethane (HCFC-142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC-134a), all in a dried whole air sample. The objective of this study is to compare calibration standards/scales and the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. The results of this study show agreement among four independent calibration scales to better than 2.5% in almost all cases, with many of the reported agreements being better than 1.0%.

Lunt, MF, Park S, Li S, Henne S, Manning AJ, Ganesan AL, Simpson IJ, Blake DR, Liang Q, O'Doherty S, Harth CM, Mühle J, Salameh PK, Weiss RF, Krummel PB, Fraser PJ, Prinn RG, Reimann S, Rigby M.  2018.  Continued emissions of the ozone-depleting substance carbon tetrachloride from Eastern Asia. Geophysical Research Letters. : Wiley-Blackwell   10.1029/2018GL079500   Abstract

Abstract Carbon tetrachloride (CCl4) is an ozone-depleting substance, accounting for about 10% of the chlorine in the troposphere. Under the terms of the Montreal Protocol, its production for dispersive uses was banned from 2010. In this work we show that, despite the controls on production being introduced, CCl4 emissions from the eastern part of China did not decline between 2009 and 2016. This finding is in contrast to a recent bottom-up estimate, which predicted a significant decrease in emissions after the introduction of production controls. We find eastern Asian emissions of CCl4 to be 16 (9?24) Gg/year on average between 2009 and 2016, with the primary source regions being in eastern China. The spatial distribution of emissions that we derive suggests that the source distribution of CCl4 in China changed during the 8-year study period, indicating a new source or sources of emissions from China's Shandong province after 2012.

Fine, RA, Smethie WM, Bullister JL, Rhein M, Min DH, Warner MJ, Poisson A, Weiss RF.  2008.  Decadal ventilation and mixing of Indian Ocean waters. Deep-Sea Research Part I-Oceanographic Research Papers. 55:20-37.   10.1016/j.dsr.2007.10.002   AbstractWebsite

Chlorofluorocarbon (CFC) and hydrographic data from the World Ocean Circulation Experiment (WOCE) Indian Ocean expedition are used to evaluate contributions to decadal ventilation of water masses. At a given density, CFC-derived ages increase and concentrations decrease from the south to north, with lowest concentrations and oldest ages in Bay of Bengal. Average ages for thermocline water are 0-40 years, and for intermediate water they are less than 10 years to more than 40 years. As compared with the marginal seas or throughflow, the most significant source of CFCs for the Indian Ocean south of 12 degrees N is the Southern Hemisphere. A simple calculation is used to show this is the case even at intermediate levels due to differences in gas solubilities and mixing of Antarctic Intermediate Water and Red Sea Water. Bottom water in the Australia-Antarctic Basin is higher in CFC concentrations than that to the west in the Enderby Basin, due to the shorter distance of this water to the Adelie Land coast and Ross Sea sources. However, by 40 degrees S, CFC concentrations in the bottom water of the Crozet Basin originating from the Weddell Sea are similar to those in the South Australia Basin. Independent observations, which show that bottom water undergoes elevated mixing between the Australia-Antarctic Basin and before entering the subtropics, are consistent with high CFC dilutions (3-14-fold) and a substantial concentration decrease (factor of 5) south to north of the Southeast Indian Ridge. CFC-bearing bottom waters with ages 30 years or more are transported into the subtropical South Indian Ocean by three western boundary currents, and highest concentrations are observed in the westernmost current. During WOCE, CFC-bearing bottom water reaches to about 30 degrees S in the Perth Basin, and to 20 degrees S in the Mascarene Basin. Comparing subtropical bottom water-CFC concentrations with those of the South Pacific and Atlantic oceans, at comparable latitudes, Indian Ocean bottom water-CFC concentrations are lower, consistent with its high dissipation rates from tidal mixing and current fluctuations as shown elsewhere. Thus, the generally high dilutions and low CFC concentrations in bottom water of the Indian Ocean are due to distance to the water mass source regions and the relative effectiveness of mixing. While it is not surprising that at thermocline, intermediate, and bottom levels, the significant ventilation sources on decadal time scales are all from the south, the CFCs show how local sources and mixing within the ocean affect the ventilation. (c) 2007 Elsevier Ltd. All rights reserved.