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2018
Vollmer, MK, Young D, Trudinger CM, Mühle 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 L, Fraser PJ, Prinn RG, Weiss RF, Simmonds PG.  2018.  Atmospheric histories and emissions of chlorofluorocarbons CFC-13 (CClF3), ΣCFC-114 (C2Cl2F4), and CFC-115 (C2ClF5). Atmospheric Chemistry and Physics. 18:979-1002.: Copernicus Publications   10.5194/acp-18-979-2018   AbstractWebsite
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Li, S, Park S, Park MK, Jo CO, Park S, Lee JY, Ha KJ, Oh H, Lee JY, Ha KJ, Oh H, Mühle J, Weiss RF, Kim KR, Montzka SA, Miller BR, Moore F, O'Doherty S, Krummel PB, Atlas E, Miller BR, Moore F, Wofsy SC.  2018.  Chemical evidence of inter-hemispheric air mass intrusion into the Northern Hemisphere mid-latitudes. Scientific Reports. 8:4669.   10.1038/s41598-018-22266-0   Abstract

The East Asian Summer Monsoon driven by temperature and moisture gradients between the Asian continent and the Pacific Ocean, leads to approximately 50% of the annual rainfall in the region across 20-40°N. Due to its increasing scientific and social importance, there have been several previous studies on identification of moisture sources for summer monsoon rainfall over East Asia mainly using Lagrangian or Eulerian atmospheric water vapor models. The major source regions for EASM previously proposed include the North Indian Ocean, South China Sea and North western Pacific. Based on high-precision and high-frequency 6-year measurement records of hydrofluorocarbons (HFCs), here we report a direct evidence of rapid intrusion of warm and moist tropical air mass from the Southern Hemisphere (SH) reaching within a couple of days up to 33°N into East Asia. We further suggest that the combination of direct chemical tracer record and a back-trajectory model with physical meteorological variables helps pave the way to identify moisture sources for monsoon rainfall. A case study for Gosan station (33.25°N, 126.19°E) indicates that the meridional transport of precipitable water from the SH accompanying the southerly/southwesterly flow contributes most significantly to its summer rainfall.[on SciFinder (R)]

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. 45:11,423-11,430.   10.1029/2018GL079500   AbstractWebsite

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.

Leedham Elvidge, E, Bönisch H, Brenninkmeijer CAM, Engel A, Fraser PJ, Gallacher E, Langenfelds R, Mühle J, Oram DE, Ray EA, Ridley AR, Röckmann T, Sturges WT, Weiss RF, Laube JC.  2018.  Evaluation of stratospheric age of air from CF4, C2F6, C3F8, CHF3, HFC-125, HFC-227ea and SF6; implications for the calculations of halocarbon lifetimes, fractional release facto. Atmospheric Chemistry and Physics. 18:3369-3385.: Copernicus Publications   10.5194/acp-18-3369-2018   AbstractWebsite

In a changing climate, potential stratospheric circulation changes require long-term monitoring. Stratospheric trace gas measurements are often used as a proxy for stratospheric circulation changes via the “mean age of air” values derived from them. In this study, we investigated five potential age of air tracers – the perfluorocarbons CF4, C2F6 andC3F8 and the hydrofluorocarbons CHF3 (HFC-23) and HFC-125 – and compare them to the traditional tracer SF6 and a (relatively) shorter-lived species, HFC-227ea. A detailed uncertainty analysis was performed on mean ages derived from these “new” tracers to allow us to confidently compare their efficacy as age tracers to the existing tracer, SF6. Our resultsshowed that uncertainties associated with the mean age derived from these new age tracers are similar to those derived from SF6, suggesting that these alternative compounds are suitable in this respect for use as age tracers. Independent verification of the suitability of these age tracers is provided by a comparison between samples analysed at the Universityof East Anglia and the Scripps Institution of Oceanography. All five tracers give younger mean ages than SF6, a discrepancy that increases with increasing mean age. Our findings qualitatively support recent work that suggests that the stratospheric lifetime of SF6 is significantly less than the previous estimate of 3200 years. The impact of these younger meanages on three policy-relevant parameters – stratospheric lifetimes, fractional release factors (FRFs) and ozone depletion potentials – is investigated in combination with a recently improved methodology to calculate FRFs. Updates to previous estimations for these parameters are provided.

Prinn, RG, Weiss RF, Arduini J, Arnold T, DeWitt HL, Fraser PJ, Ganesan AL, Gasore J, Harth CM, Hermansen O, Kim J, Krummel PB, Li S, Loh ZM, Lunder CR, Maione M, Manning AJ, Miller BR, Mitrevski B, Mühle J, O'Doherty S, Park S, Reimann S, Rigby M, Saito T, Salameh PK, Schmidt R, Simmonds PG, Steele LP, Vollmer MK, Wang RH, Yao B, Yokouchi Y, Young D, Zhou L.  2018.  History of chemically and radiatively important atmospheric gases from the Advanced Global Atmospheric Gases Experiment (AGAGE). Earth Syst. Sci. Data. 10:985-1018.: Copernicus Publications   10.5194/essd-10-985-2018   AbstractWebsite
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Arnold, T, Manning AJ, Kim J, Li S, Webster H, Thomson D, Mühle J, Weiss RF, Park S, O'Doherty S.  2018.  Inverse modelling of CF4 and NF3 emissions in East Asia. Atmospheric Chemistry and Physics. 18:13305-13320.: Copernicus Publications   10.5194/acp-18-13305-2018   AbstractWebsite
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Simmonds, PG, Rigby M, McCulloch A, Vollmer MK, Henne S, Mühle J, O'Doherty S, Manning AJ, Krummel PB, Fraser PJ, Young D, Weiss RF, Salameh PK, Harth CM, Reimann S, Trudinger CM, Steele P, 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.: Copernicus Publications   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 Mt CO2 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 2010–2016 were 89 ± 2 Gg (1.1 ± 0.2 Gt CO2 eq.), which led to an increase in radiative forcing of 1.0 ± 0.1 mW m−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  ∼  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.

Park, S, Li S, Mühle J, O'Doherty S, Weiss RF, Fang X, Reimann S, Prinn RG.  2018.  Toward resolving the budget discrepancy of ozone-depleting carbon tetrachloride (CCl4): an analysis of top-down emissions from China. Atmospheric Chemistry and Physics. 18:11729-11738.: Copernicus Publications   10.5194/acp-18-11729-2018   AbstractWebsite
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2017
Dlugokencky, EJ, Hall BD, Montzka SA, Dutton G, Mühle J, Elkins JW.  2017.  [Global Climate, Atmospheric composition] Long-lived greenhouse gases [in State of the Climate in 2016]. Bulletin of the American Meteorological Society. 98( Blunden J, Arndt DS, Eds.).:S43-S46. Abstract
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Rigby, M, Montzka SA, Prinn RG, White JWC, Young D, O’Doherty S, Lunt MF, Ganesan AL, Manning AJ, Simmonds PG, Salameh PK, Harth CM, Mühle J, Weiss RF, Fraser PJ, Steele PL, Krummel PB, McCulloch A, Park S.  2017.  Role of atmospheric oxidation in recent methane growth. Proceedings of the National Academy of Sciences.   10.1073/pnas.1616426114   AbstractWebsite

The growth in global methane (CH4) concentration, which had been ongoing since the industrial revolution, stalled around the year 2000 before resuming globally in 2007. We evaluate the role of the hydroxyl radical (OH), the major CH4 sink, in the recent CH4 growth. We also examine the influence of systematic uncertainties in OH concentrations on CH4 emissions inferred from atmospheric observations. We use observations of 1,1,1-trichloroethane (CH3CCl3), which is lost primarily through reaction with OH, to estimate OH levels as well as CH3CC3 emissions, which have uncertainty that previously limited the accuracy of OH estimates. We find a 64–70% probability that a decline in OH has contributed to the post-2007 methane rise. Our median solution suggests that CH4 emissions increased relatively steadily during the late 1990s and early 2000s, after which growth was more modest. This solution obviates the need for a sudden statistically significant change in total CH4 emissions around the year 2007 to explain the atmospheric observations and can explain some of the decline in the atmospheric 13CH4/12CH4 ratio and the recent growth in C2H6. Our approach indicates that significant OH-related uncertainties in the CH4 budget remain, and we find that it is not possible to implicate, with a high degree of confidence, rapid global CH4 emissions changes as the primary driver of recent trends when our inferred OH trends and these uncertainties are considered.

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

Abstract 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).

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. Atmospheric Chemistry and Physics. 17:4641-4655.: Copernicus Publications   10.5194/acp-17-4641-2017   AbstractWebsite
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Liang, Q, Chipperfield MP, Fleming EL, Abraham LN, Braesicke P, Burkholder JB, Daniel JS, Dhomse S, Fraser PJ, Hardiman SC, Jackman CH, Kinnison DE, Krummel PB, Montzka SA, Morgenstern O, McCulloch A, Mühle J, Newman PA, Orkin VL, Pitari G, Prinn RG, Rigby M, Rozanov E, Stenke A, Tummon F, Velders GJM, Visioni D, Weiss RF.  2017.  Deriving Global OH Abundance and Atmospheric Lifetimes for Long-Lived Gases: A Search for CH3CCl3 Alternatives. Journal of Geophysical Research: Atmospheres. 122:11914-11933.   10.1002/2017jd026926   AbstractWebsite

An accurate estimate of global hydroxyl radical (OH) abundance is important for projections of air quality, climate, and stratospheric ozone recovery. As the atmospheric mixing ratios of methyl chloroform (CH3CCl3) (MCF), the commonly used OH reference gas, approaches zero, it is important to find alternative approaches to infer atmospheric OH abundance and variability. The lack of global bottom-up emission inventories is the primary obstacle in choosing a MCF alternative. We illustrate that global emissions of long-lived trace gases can be inferred from their observed mixing ratio differences between the Northern Hemisphere (NH) and Southern Hemisphere (SH), given realistic estimates of their NH-SH exchange time, the emission partitioning between the two hemispheres, and the NH versus SH OH abundance ratio. Using the observed long-term trend and emissions derived from the measured hemispheric gradient, the combination of HFC-32 (CH2F2), HFC-134a (CH2FCF3, HFC-152a (CH3CHF2), and HCFC-22 (CHClF2), instead of a single gas, will be useful as a MCF alternative to infer global and hemispheric OH abundance and trace gas lifetimes. The primary assumption on which this multispecies approach relies is that the OH lifetimes can be estimated by scaling the thermal reaction rates of a reference gas at 272 K on global and hemispheric scales. Thus, the derived hemispheric and global OH estimates are forced to reconcile the observed trends and gradient for all four compounds simultaneously. However, currently, observations of these gases from the surface networks do not provide more accurate OH abundance estimate than that from MCF.

2016
Chipperfield, MP, Liang Q, Rigby M, Hossaini R, Montzka SA, Dhomse S, Feng WH, Prinn RG, Weiss RF, Harth CM, Salameh PK, Muhle J, O'Doherty S, Young D, Simmonds PG, Krummel PB, Fraser PJ, Steele LP, Happell JD, Rhew RC, Butler J, Yvon-Lewis SA, Hall B, Nance D, Moore F, Miller BR, Elkins J, Harrison JJ, Boone CD, Atlas EL, Mahieu E.  2016.  Model sensitivity studies of the decrease in atmospheric carbon tetrachloride. Atmospheric Chemistry and Physics. 16:15741-15754.   10.5194/acp-16-15741-2016   AbstractWebsite

Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74% of total), but a reported 10% uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9% of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17% of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year(-1), the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year(-1). Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks.

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.

Trudinger, CM, Fraser PJ, Etheridge DM, Sturges WT, Vollmer MK, Rigby M, Martinerie P, Mühle J, Worton DR, Krummel PB, Steele LP, Miller BR, Laube J, Mani FS, Rayner PJ, Harth CM, Witrant E, Blunier T, Schwander J, O'Doherty S, Battle M.  2016.  Atmospheric abundance and global emissions of perfluorocarbons CF4, C2F6 and C3F8 since 1800 inferred from ice core, firn, air archive and in situ measurements. Atmospheric Chemistry and Physics. 16:11733-11754.: Copernicus Publications   10.5194/acp-16-11733-2016   AbstractWebsite
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Simmonds, PG, Rigby M, Manning AJ, Lunt MF, O'Doherty S, McCulloch A, Fraser PJ, Henne S, Vollmer MK, Mühle J, Weiss RF, Salameh PK, Young D, Reimann S, Wenger A, Arnold T, Harth CM, Krummel PB, Steele LP, Dunse BL, Miller BR, Lunder CR, Hermansen O, Schmidbauer N, Saito T, Yokouchi Y, Park S, Li S, Yao B, Zhou LX, Arduini J, Maione M, Wang RHJ, Ivy D, Prinn RG.  2016.  Global and regional emissions estimates of 1,1-difluoroethane (HFC-152a, CH3CHF2) from in situ and air archive observations. Atmospheric Chemistry and Physics. 16:365-382.: Copernicus Publications   10.5194/acp-16-365-2016   AbstractWebsite
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Chirkov, M, Stiller GP, Laeng A, Kellmann S, von Clarmann T, Boone CD, Elkins JW, Engel A, Glatthor N, Grabowski U, Harth CM, Kiefer M, Kolonjari F, Krummel PB, Linden A, Lunder CR, Miller BR, Montzka SA, Mühle J, O'Doherty S, Orphal J, Prinn RG, Toon G, Vollmer MK, Walker KA, Weiss RF, Wiegele A, Young D.  2016.  Global HCFC-22 measurements with MIPAS: retrieval, validation, global distribution and its evolution over 2005–2012. Atmospheric Chemistry and Physics. 16:3345-3368.: Copernicus Publications   10.5194/acp-16-3345-2016   AbstractWebsite
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2015
Lunt, MF, Rigby M, Ganesan AL, Manning AJ, Prinn RG, O’Doherty S, Mühle J, Harth CM, Salameh PK, Arnold T, Weiss RF, Saito T, Yokouchi Y, Krummel PB, Steele PL, Fraser PJ, Li S, Park S, Reimann S, Vollmer MK, Lunder C, Hermansen O, Schmidbauer N, Maione M, Arduini J, Young D, Simmonds PG.  2015.  Reconciling reported and unreported HFC emissions with atmospheric observations. Proceedings of the National Academy of Sciences. 112(9):5927-5931.   10.1073/pnas.1420247112   AbstractWebsite

We infer global and regional emissions of five of the most abundant hydrofluorocarbons (HFCs) using atmospheric measurements from the Advanced Global Atmospheric Gases Experiment and the National Institute for Environmental Studies, Japan, networks. We find that the total CO2-equivalent emissions of the five HFCs from countries that are required to provide detailed, annual reports to the United Nations Framework Convention on Climate Change (UNFCCC) increased from 198 (175–221) Tg-CO2-eq⋅y–1 in 2007 to 275 (246–304) Tg-CO2-eq⋅y–1 in 2012. These global warming potential-weighted aggregated emissions agree well with those reported to the UNFCCC throughout this period and indicate that the gap between reported emissions and global HFC emissions derived from atmospheric trends is almost entirely due to emissions from nonreporting countries. However, our measurement-based estimates of individual HFC species suggest that emissions, from reporting countries, of the most abundant HFC, HFC-134a, were only 79% (63–95%) of the UNFCCC inventory total, while other HFC emissions were significantly greater than the reported values. These results suggest that there are inaccuracies in the reporting methods for individual HFCs, which appear to cancel when aggregated together.

Hossaini, R, Chipperfield MP, Saiz-Lopez A, Harrison JJ, von Glasow R, Sommariva R, Atlas E, Navarro M, Montzka SA, Feng W, Dhomse S, Harth C, Mühle J, Lunder C, O'Doherty S, Young D, Reimann S, Vollmer MK, Krummel PB, Bernath GPFC.  2015.  Growth in stratospheric chlorine from short-lived chemicals not controlled by the Montreal Protocol. Geophysical Research Letters. 42(11):4573-4580.   10.1002/2015gl063783   AbstractWebsite

We have developed a chemical mechanism describing the tropospheric degradation of chlorine-containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS (ClyVSLS) between 2005 to 2013. By constraining the model with surface measurements of chloroform (CHCl3), dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), trichloroethene (C2HCL3) and 1,2-dichloroethane (CH2ClCH2Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection of source gases dominates this supply, accounting for ~83% of the total. The remainder comes from VSLS-derived organic products, phosgene (COCl2, 7%) and formyl chloride (CHClO, 2%), and also hydrogen chloride (HCl, 8%). Stratospheric ClyVSLS increased by ~52% between 2005-2013, with a mean growth rate of 3.7 ppt Cl/yr. This increase is due to recent and ongoing growth in anthropogenic CH – the most abundant chlorinated VSLS not controlled by the Montreal Protocol.

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. Elementa: Science of the Anthropocene. 3:1-13.   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%.

Johnson, TL, Brahamsha B, Palenik B, Mühle J.  2015.  Halomethane production by vanadium-dependent bromoperoxidase in marine Synechococcus. Limnology and Oceanography. 60:1823-1835.   10.1002/lno.10135   AbstractWebsite

To investigate the role of vanadium-dependent bromoperoxidase (VBPO) for the production of halogenated methanes in marine prokaryotes, we measured VBPO activity and halomethane production in two strains of Synechococcus; one with VBPO (strain CC9311) and one without VBPO (strain WH8102). A mutant strain of CC9311, VMUT2, in which the gene for VBPO is disrupted, was also tested. A suite of halomethanes was measured in the headspace above cultures as well as in the culture medium with a purge-and-trap method. Monohalomethanes were the most consistently produced molecules among the three strains tested. Additionally, CC9311 produced 301 ± 109 molecules cell−1 d−1 of bromoform (CHBr3) when VBPO activity was detected, while production was not significantly different from zero when VBPO activity was not detected. VBPO activity and CHBr3 production were only detected when cultures of CC9311 were stirred, which may contribute to the often moderate to weak correlations between CHBr3 concentration and biological markers in the ocean. No production was seen by VMUT2 or WH8102. These data show that CHBr3 production rates are dramatically increased with or exclusive to the presence of VBPO, supporting its involvement in CHBr3 synthesis. This study thus provides genetic evidence that certain strains of marine Synechococcus, under particular conditions, can be a natural source of marine CHBr3, which contributes to ozone depletion in the stratosphere.

Deeds, DA, Kulongoski JT, Mühle J, Weiss RF.  2015.  Tectonic activity as a significant source of crustal tetrafluoromethane emissions to the atmosphere: Observations in groundwaters along the San Andreas Fault. Earth and Planetary Science Letters. 412:163-172.   http://dx.doi.org/10.1016/j.epsl.2014.12.016   AbstractWebsite

Abstract Tetrafluoromethane (CF4) concentrations were measured in 14 groundwater samples from the Cuyama Valley, Mil Potrero and Cuddy Valley aquifers along the Big Bend section of the San Andreas Fault System (SAFS) in California to assess whether tectonic activity in this region is a significant source of crustal CF4 to the atmosphere. Dissolved CF4 concentrations in all groundwater samples but one were elevated with respect to estimated recharge concentrations including entrainment of excess air during recharge ( C r e ; ∼30 fmol kg−1 H2O), indicating subsurface addition of CF4 to these groundwaters. Groundwaters in the Cuyama Valley contain small CF4 excesses (0.1–9 times C r e ), which may be attributed to an in situ release from weathering and a minor addition of deep crustal CF4 introduced to the shallow groundwater through nearby faults. CF4 excesses in groundwaters within 200 m of the SAFS are larger (10–980 times C r e ) and indicate the presence of a deep crustal flux of CF4 that is likely associated with the physical alteration of silicate minerals in the shear zone of the SAFS. Extrapolating CF4 flux rates observed in this study to the full extent of the SAFS (1300 km × 20–100 km) suggests that the SAFS potentially emits ( 0.3 – 1 ) × 10 − 1 kg CF4 yr−1 to the Earth's surface. For comparison, the chemical weathering of ∼ 7.5 × 10 4 km 2 of granitic rock in California is estimated to release ( 0.019 – 3.2 ) × 10 − 1 kg CF4 yr−1. Tectonic activity is likely an important, and potentially the dominant, driver of natural emissions of CF4 to the atmosphere. Variations in preindustrial atmospheric CF4 as observed in paleo-archives such as ice cores may therefore represent changes in both continental weathering and tectonic activity, including changes driven by variations in continental ice cover during glacial–interglacial transitions.

Dlugokencky, EJ, Hall BD, Montzka SA, Dutton G, Mühle J, Elkins JW.  2015.  [Global Climate, Atmospheric chemical composition] Long-lived greenhouse gases [in State of the Climate in 2014]. Bulletin of the American Meteorological Society. 96( Blunden J, Arndt DS, Eds.).:S39-S42. Abstract
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2014
O'Doherty, S, Rigby M, Muhle J, Ivy DJ, Miller BR, Young D, Simmonds PG, Reimann S, Vollmer MK, Krummel PB, Fraser PJ, Steele LP, Dunse B, Salameh PK, Harth CM, Arnold T, Weiss RF, Kim J, Park S, Li S, Lunder C, Hermansen O, Schmidbauer N, Zhou LX, Yao B, Wang RHJ, Manning AJ, Prinn RG.  2014.  Global emissions of HFC-143a (CH3CF3) and HFC-32 (CH2F2) from in situ and air archive atmospheric observations. Atmospheric Chemistry and Physics. 14:9249-9258.   10.5194/acp-14-9249-2014   AbstractWebsite

High-frequency, in situ observations from the Advanced Global Atmospheric Gases Experiment (AGAGE), for the period 2003 to 2012, combined with archive flask measurements dating back to 1977, have been used to capture the rapid growth of HFC-143a (CH3CF3) and HFC-32 (CH2F2) mole fractions and emissions into the atmosphere. Here we report the first in situ global measurements of these two gases. HFC-143a and HFC-32 are the third and sixth most abundant hydrofluorocarbons (HFCs) respectively and they currently make an appreciable contribution to the HFCs in terms of atmospheric radiative forcing (1.7 +/- 0.04 and 0.7 +/- 0.02 mW m(-2) in 2012 respectively). In 2012 the global average mole fraction of HFC-143a was 13.4 +/- 0.3 ppt (1 sigma) in the lower troposphere and its growth rate was 1.4 +/- 0.04 ppt yr(-1); HFC-32 had a global mean mole fraction of 6.2 +/- 0.2 ppt and a growth rate of 1.1 +/- 0.04 ppt yr(-1) in 2012. The extensive observations presented in this work have been combined with an atmospheric transport model to simulate global atmospheric abundances and derive global emission estimates. It is estimated that 23 +/- 3 Gg yr(-1) of HFC-143a and 21 +/- 11 Gg yr(-1) of HFC-32 were emitted globally in 2012, and the emission rates are estimated to be increasing by 7 +/- 5% yr(-1) for HFC-143a and 14 +/- 11% yr(-1) for HFC-32.