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Patra, PK, Krol MC, Montzka SA, Arnold T, Atlas EL, Lintner BR, Stephens BB, Xiang B, Elkins JW, Fraser PJ, Ghosh A, Hintsa EJ, Hurst DF, Ishijima K, Krummel PB, Miller BR, Miyazaki K, Moore FL, Muhle J, O'Doherty S, Prinn RG, Steele LP, Takigawa M, Wang HJ, Weiss RF, Wofsy SC, Young D.  2014.  Observational evidence for interhemispheric hydroxyl-radical parity. Nature. 513:219-+.   10.1038/nature13721   AbstractWebsite

The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere(1-3). The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species such as nitrogen oxides and methane(4-6). It remains poorly constrained, however, with a range of estimates from 0.85 to 1.4 (refs 4,7-10). Here we determine the NH/SH ratio of OH with the help of methyl chloroform data (a proxy for OH concentrations) and an atmospheric transport model that accurately describes interhemispheric transport and modelled emissions. We find that for the years 2004-2011 the model predicts an annual mean NH-SH gradient of methyl chloroform that is a tight linear function of the modelled NH/SH ratio in annual mean OH. We estimate a NH/SH OH ratio of 0.97 +/- 0.12 during this time period by optimizing global total emissions and mean OH abundance to fit methyl chloroform data from two surface-measurement networks and aircraft campaigns(11-13). Our findings suggest that top-down emission estimates of reactive species such as nitrogen oxides in key emitting countries in the NH that are based on a NH/SH OH ratio larger than 1 may be overestimated.

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.

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.

Huang, J, Golombek A, Prinn R, Weiss R, Fraser P, Simmonds P, Dlugokencky EJ, Hall B, Elkins J, Steele P, Langenfelds R, Krummel P, Dutton G, Porter L.  2008.  Estimation of regional emissions of nitrous oxide from 1997 to 2005 using multinetwork measurements, a chemical transport model, and an inverse method. Journal of Geophysical Research-Atmospheres. 113   10.1029/2007jd009381   AbstractWebsite

Nitrous oxide (N2O) is an important ozone-depleting gas and greenhouse gas with multiple uncertain emission processes. Global nitrous oxide observations, the Model of Atmospheric Transport and Chemistry (MATCH) and an inverse method were used to optimally estimate N2O emissions from twelve source regions around the globe. MATCH was used with forecast center reanalysis winds at T62 resolution (192 longitude by 94 latitude surface grid, and 28 vertical levels) from 1 July 1996 to 30 June 2006. The average concentrations of N2O in the lowest four layers of the model were then compared with the monthly mean observations from four national/international networks measuring at 65 surface sites. A 12-month-running-mean smoother was applied to both the model results and the observations, due to the fact that the model was not able to reproduce the very small observed seasonal cycles. The inverse method was then used to solve for the time-averaged regional emissions of N2O for two time periods (1 January 1997 to 31 December 2001 and 1 January 2002 to 31 December 2005). The best estimate inversions assume that the model stratospheric destruction rates, which lead to a global N2O lifetime of 125 years, are correct. It also assumes normalized emission spatial distributions within each region from Bouwman et al. (1995). We conclude that global N2O emissions with 66% probability errors are 16.3(-1.2)(+1.5) and 15.4(-1.3)(+1.7) TgN (N2O) a(-1), for 1997-2001 and 2001-2005 respectively. Emissions from the equator to 30 degrees N increased significantly from the initial Bouwman et al. (1995) estimates while emissions from southern oceans (30 degrees S-90 degrees S) decreased significantly. The quoted uncertainties include both the measurement errors and modeling uncertainties estimated using a separate flexible 12-box model. We also found that 23 +/- 4% of the N2O global total emissions come from the ocean, which is slightly smaller than the Bouwman et al. (1995) estimate. For the estimation of emissions from the twelve model regions, we conclude that, relative to Bouwman et al. (1995), land emissions from South America, Africa, and China/Japan/South East Asia are larger, while land emissions from Australia/New Zealand are smaller. Our study also shows a shift of the oceanic sources from the extratropical to the tropical oceans relative to Bouwman et al. (1995). Between the periods 1997-2001 and 2002-2005, emissions increased in China/Japan/South East Asia, 0 degrees-30 degrees N oceans, and North West Asia and decreased in Australia/New Zealand, 30 degrees S-90 degrees S oceans, 30 degrees N-90 degrees N oceans, and Africa. The lower tropical ocean emissions in 1997-2001 relative to 2002-2005 could result from the effects of the 1997-1998 El Nino in the earlier period.

Prinn, RG, Huang J, Weiss RF, Cunnold DM, Fraser PJ, Simmonds PG, McCulloch A, Harth C, Reimann S, Salameh P, O'Doherty S, Wang RHJ, Porter LW, Miller BR, Krummel PB.  2005.  Evidence for variability of atmospheric hydroxyl radicals over the past quarter century. Geophysical Research Letters. 32   10.1029/2004gl022228   AbstractWebsite

The hydroxyl free radical (OH) is the major oxidizing chemical in the atmosphere, destroying about 3.7 petagrams (Pg) of trace gases each year, including many gases involved in ozone depletion, the greenhouse effect and urban air pollution. Measurements of 1,1,1-trichloroethane (methyl chloroform, CH3CCl3), which reacts with OH, provide the most accurate method currently utilized for determining the global behavior of OH. We report that CH3CCl3 levels rose steadily from 1978 to reach a maximum in 1992 and have since decreased rapidly to levels in 2004 about 30% of the levels when measurements began in 1978. Analysis of these observations shows that global average OH levels had a small maximum around 1989 and a larger minimum around 1998, with OH concentrations in 2003 being comparable to those in 1979. This post-1998 recovery of OH reported here contrasts with the situation 4 years ago when reported OH was decreasing. The 1997-1999 OH minimum coincides with, and is likely caused by, major global wildfires and an intense El Nino event at this time.

Rhew, RC, Miller BR, Vollmer MK, Weiss RF.  2001.  Shrubland fluxes of methyl bromide and methyl chloride. Journal of Geophysical Research-Atmospheres. 106:20875-20882.   10.1029/2001jd000413   AbstractWebsite

Flux measurements in coastal sage scrub, chamise chaparral, and creosote bush scrub environments show that methyl bromide (CH(3)Br) and methyl chloride (CH(3)Cl), compounds that are involved in stratospheric ozone depletion, are both produced and consumed by southern California shrubland ecosystems. CH(3)Br and CH(3)Cl are produced in association with a variety of plants and are consumed by the soils, although there is a large variability in the fluxes, depending on predominant vegetation and environmental conditions. At sites with a net uptake of both compounds the fluxes of CH(3)Cl and CH(3)Br show a strong correlation, with a molar ratio of roughly 40:1, pointing to a similar mechanism of consumption. In contrast, the net production rates of these compounds show no apparent correlation with each other. The average observed net CH(3)Br uptake rates are an order of magnitude smaller than the previously reported average soil consumption rates assigned to shrublands. Extrapolations from our field measurements suggest that shrublands globally have a maximum net consumption of <1 Gg yr(-1) for CH(3)Br and < 20 Gg yr(-1) for CH(3)Cl and may, in fact, be net sources for these compounds. Consequently, the measured net fluxes from shrubland ecosystems can account for part of the present imbalance in the CH(3)Br budget by adding a new source term and potentially reducing the soil sink term. These results also suggest that while shrubland soil consumption of CH(3)Cl may be small, soils in general may be a globally significant sink for CH(3)Cl.

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.

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.

Falkner, KK, Measures CI, Herbelin SE, Edmond JM, Weiss RF.  1991.  The major and minor element geochemistry of Lake Baikal. Limnology and Oceanography. 36:413-423. AbstractWebsite

A comprehensive, joint Soviet-American study of the chemistry of Lake Baikal, the world's deepest (1,632 m) lake, was carried out in July 1988. In this paper, we report the major, minor, and preliminary trace element concentrations for three profiles obtained at or near the deepest and central part of the three major basins of the lake. With the exception of Ba, the distributions of major and minor elements were homogeneous, displaying no variations greater than analytical uncertainties. Average concentrations in mu-mol kg-1 (1 SD) are titration alkalinity = 1,093(6), SO42- = 57.4(1.3), Cl = 12.3(0.7), Ca = 402(7), Mg = 126(1), Na = 155(4), and K = 24.1(1.0); and in nmol kg-1 are Sr = 1,350(30), Li = 296(12), Ba = 74.7(2.6), Rb = 7.10(0.23), and U = 1.77(0.12). Excluding K and Cl, these values compare favorably with previously published results. Although some hydrothermal activity is known to occur within the lake, it does not appear to significantly affect major ion cycling. The residence times of the major ions are 330 yr or the same as that of water in the basin and so are controlled predominantly by their riverine fluxes. There is not yet enough information to assess whether hydrothermal processes affect minor element cycles. Ba concentrations decrease with depth, showing abrupt decreases near the bottom at two stations. It appears to undergo some form of uptake at the sediments, but further study is required to discern the processes governing Ba distribution.